Benzochromene derivatives

ABSTRACT

The present invention relates to benzochromene derivatives of the formula I 
                         
where the various parameters have the meaning indicated in the text, and to liquid-crystal media which comprise these compounds, and to the use of the media in electro-optical displays, in particular in VAN-LCDs, and to the use of the compounds and physiologically acceptable derivatives thereof as therapeutic active ingredients.

The present invention relates to benzochromene derivatives, preferably mesogenic benzochromene derivatives, in particular liquid-crystalline benzochromene derivatives, and to liquid-crystalline media comprising these benzochromene derivatives. The present invention furthermore relates to liquid-crystal displays, in particular active matrix addressed liquid-crystal displays (AMDs or AM LCDs) and very particularly so-called VAN (“vertically aligned nematic”) liquid-crystal displays, an embodiment of ECB (“electrically controlled birefringence”) liquid-crystal displays, in which nematic liquid crystals of negative dielectric anisotropy (Δ∈) are used.

In liquid-crystal displays of this type, the liquid crystals are used as dielectrics, whose optical properties change reversibly on application of an electric voltage. Electro-optical displays which use liquid crystals as media are known to the person skilled in the art. These liquid-crystal displays use various electro-optical effects. The commonest thereof are the TN (“twisted nematic”) effect, with a homogeneous, virtually planar initial alignment of the liquid-crystal director and a nematic structure which is twisted by about 90°, the STN (“super-twisted nematic”) effect and the SBE (“supertwisted birefringence effect”) with a nematic structure which is twisted by 180° or more. In these and similar electro-optical effects, liquid-crystalline media of positive dielectric anisotropy (Δ∈) are used.

Besides the said electro-optical effects, which require liquid-crystal media of positive dielectric anisotropy, there are other electro-optical effects which use liquid-crystal media of negative dielectric anisotropy, such as, for example, the ECB effect and its sub-forms DAP (“deformation of aligned phases”), VAN and CSH (“colour super homeotropics”).

An electro-optical effect having excellent, low viewing-angle dependence of the contrast uses axially symmetrical micropixels (ASMs). In this effect, the liquid crystal of each pixel is surrounded in a cylindrical manner by a polymer material. This mode is particularly suitable for combination with addressing through plasma channels. Thus, in particular, large-area PA (“plasma addressed”) LCDs having good viewing-angle dependence of the contrast can be achieved.

The IPS (“in plane switching”) effect employed to an increased extent recently can use both dielectrically positive and also dielectrically negative liquid-crystal media, in a similar manner to “guest/host” displays, which can employ dyes either in dielectrically positive or dielectrically negative media, depending on the display mode used.

Since the operating voltage in liquid-crystal displays in general, i.e. also in displays utilising these effects, should be as low as possible, use is made of liquid-crystal media having a large absolute value of the dielectric anisotropy which generally predominantly and in most cases even essentially consist of liquid-crystal compounds having a dielectric anisotropy having the corresponding sign, i.e. of compounds of positive dielectric anisotropy in the case of dielectrically positive media and of compounds of negative dielectric anisotropy in the case of dielectrically negative media. In the respective types of media (dielectrically positive or dielectrically negative), at most significant amounts of dielectrically neutral liquid-crystal compounds are typically employed. Liquid-crystal compounds having the opposite sign of the dielectric anisotropy to that of the dielectric anisotropy of the medium are generally employed extremely sparingly or not at all.

An exception is formed here by liquid-crystalline media for MIM (“metal-insulator-metal”) displays (Simmons, J. G., Phys. Rev. 155 No. 3, pp. 657-660 and Niwa, J. G. et al., SID 84 Digest, pp. 304-307, June 1984), in which the liquid-crystal media are addressed by means of an active matrix of thin-film transistors. In this type of addressing, which utilises the non-linear characteristic line of diode switching, a storage capacitor cannot be charged together with the electrodes of the liquid-crystal display elements (pixels), in contrast to TFT displays. In order to reduce the effect of the drop in voltage during the addressing cycle, the largest possible base value of the dielectric constant is thus necessary. In the case of dielectrically positive media, as employed, for example, in MIM-TN displays, the dielectric constant perpendicular to the molecular axis (∈_(⊥)) must thus be as large as possible since it determines the basic capacitance of the pixel. To this end, as described, for example, in WO 93/01253, EP 0 663 502 and DE 195 21 483, compounds of negative dielectric anisotropy are simultaneously also employed besides dielectrically positive compounds in the dielectrically positive liquid-crystal media.

A further exception is formed by STN displays, in which, for example, dielectrically positive liquid-crystal media comprising dielectrically negative liquid-crystal compounds in accordance with DE 41 00 287 are employed in order to increase the steepness of the electro-optical characteristic line.

The pixels of the liquid-crystal displays can be addressed directly, time-sequentially, i.e. in time multiplex mode, or by means of a matrix of active elements having nonlinear electrical characteristic lines.

The commonest AMDs to date use discrete active electronic switching elements, such as, for example, three-pole switching elements, such as MOS (“metal oxide silicon”) transistors or thin film transistors (TFTs) or varistors, or 2-pole switching elements, such as, for example, MIM (“metal-insulator-metal”) diodes, ring diodes or “back-to-back” diodes. Various semiconductor materials, predominantly silicon, but also cadmium selenide, are used in the TFTs. In particular, amorphous silicon or polycrystalline silicon is used.

In accordance with the present application, preference is given to liquid-crystal displays having an electric field perpendicular to the liquid-crystal layer and liquid-crystal media of negative dielectric anisotropy (Δ∈<0). In these displays, the edge alignment of the liquid crystals is homeotropic. In the fully switched-on state, i.e. on application of an electric voltage of appropriate magnitude, the liquid-crystal director is aligned parallel to the layer plane.

Benzochromene derivatives, for example of the following three formulae

-   -   in which     -   R¹ and R² denote, for example, alkyl,         are disclosed in DE 10 2002 004 228.4 and JP2005120073. These         compounds are characterised by very high absolute values of the         dielectric anisotropy and, as a consequence of the biphenyl         partial structure, have very high birefringence. Owing to the         different requirements of the physical properties of         liquid-crystal mixtures, it is necessary also to provide         substances having lower birefringence, in particular, for         example, for reflective displays. This applies, in particular,         to the VA mode, since the lateral substitution by polar groups         generally takes place on aromatic rings. It can thus be seen         that there is both a demand for further mesogenic compounds and         also, in particular, a demand for liquid-crystal media of         negative dielectric anisotropy, a large absolute value of the         dielectric anisotropy, a value of the optical anisotropy (Δn)         corresponding to the particular application, a broad nematic         phase, good stability to UV, heat and electric voltage, and low         rotational viscosity.

This is achieved through the use of the mesogenic compounds of the formula I according to the invention

-   -   in which     -   Y denotes —CO—, CS, —CH₂— or —CF₂—, preferably CH₂ or CF₂,     -   L denotes H, halogen or CF₃, preferably H, F or Cl, particularly         preferably H or F and very particularly preferably F,

-   -    each, independently of one another and, if present more than         once, also these independently of one another, denote     -   (a) a trans-1,4-cyclohexylene radical, in which, in addition,         one or two non-adjacent CH₂ groups may be replaced by —O— and/or         —S—,     -   (b) a 1,4-cyclohexenylene radical,     -   (c) a 1,4-phenylene radical, in which, in addition, one or two         non-adjacent CH groups may be replaced by N, or     -   (d) naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and         1,2,3,4-tetrahydronaphthalene-2,6-diyl,     -   (e) a radical selected from the group         1,4-bicyclo[2.2.2]octylene, 1,3-bicyclo[1.1.1]pentylene and         spiro[3.3]heptane-2,6-diyl, where in         -   (a) and (b), one or more —CH₂— groups, independently of one             another, may each be replaced by a —CHF— or —CF₂— group, and             in         -   (c) and (d), one or more —CH═ groups, independently of one             another, may each be replaced by a —CF═, —C(CN)═, —C(CH₃)═,             —C(CH₂F)═, —C(CHF₂)═, —C(O—CH₃)═, —C(O—CHF₂)═ or —C(O—CF₃)═             group, preferably a —CF═ group, and preferably denote

-   -    denotes a 1,4-trans-cyclohexane-1,2,4-triyl radical, in which,         in addition, one or two non-adjacent CH₂ groups may be replaced         by —O— and/or —S—, and one or more —CH₂— groups, in each case         independently of one another, may each be replaced by a —CHF— or         —CF₂— group, and the —CH< group may be replaced by a —CF< group,         and which may optionally contain one or two C—C double bonds,         where, in this case, one or more —CH═ groups, independently of         one another, may each be replaced by a —CF═, —C(CN)═, —C(CH₃)═,         —C(CH₂F)═, —C(CHF₂)═, —C(O—CH₃)═, —C(O—CHF₂)═ or —C(O—CF₃)═         group, preferably a —CF═ group,     -   R¹ and R² each, independently of one another, denote H, halogen,         —CN, —SCN, —SF₅, —CF₃, —CHF₂, —CH₂F, —OCF₃, —OCHF₂, an alkyl         group having 1 to 15 C atoms which is monosubstituted by CN or         CF₃ or at least mono-substituted by halogen, where, in addition,         one or more CH₂ groups, in each case independently of one         another, may be replaced by —O—, —S—, —CH═CH—, —CF═CF—, —CF═CH—,         —CH═CF—,

-   -    —CO—, —CO—O—, —O—CO— or —O—CO—O— in such a way that neither O         nor S atoms are linked directly to one another,     -   preferably one of     -   R¹ and R² denotes alkyl or alkoxy having 1 to 12 C atoms,         alkoxyalkyl, alkenyl or alkenyloxy having 2 to 12 C atoms and         the other, independently of the first, likewise denotes alkyl         and alkoxy having 1 to 12 C atoms, alkoxyalkyl, alkenyl or         alkenyloxy having 2 to 12 C atoms or also F, Cl, Br, —CN, —SCN,         —SF₅, —CF₃, —CHF₂, —CH₂F, —OCF₃ or —OCHF₂     -   Z¹ and Z² each, independently of one another and, if present         more than once, also these independently of one another, denote         —CH₂—CH₂—, —CF₂—CF₂—, —CF₂—CH₂—, —CH₂—CF₂—, —CH═CH—, —CF═CF—,         —CF═CH—, —CH═CF—, —C≡C—, —COO—, —OCO—, —CH₂O—, —OCH₂—, —CF₂O—,         —OCF₂—, or a combination of two of these groups, where no two O         atoms are bonded to one another,     -   preferably —(CH₂)₄—, —CH₂—CH₂—, —CF₂—CF₂—, —CH═CH—, —CF═CF—,         —C≡C—, —CH₂O—, —CF₂O— or a single bond,     -   particularly preferably —CH₂O—, —CH₂—CH₂—, —CF₂—CF₂—, —CF═CF—,         —CF₂O— or a single bond, and     -   n and m each denote 0, 1 or 2, where     -   n+m denotes 0, 1, 2 or 3, preferably 0, 1 or 2, particularly         preferably 0 or 1.

Particular preference is given to liquid-crystal compounds of the formula I of the sub-formulae I-1 to I-3

in which the parameters have the meanings given above under formula I, and

-   -   L preferably denotes F.

Preference is given to compounds of the formula I, preferably selected from the group of the compounds of the formulae I-1 to I-3, in which

-   the sum n+m is 0 or 1, preferably 0.

A preferred embodiment is represented by the compounds of the formula I in which the sum n+m is 1 and preferably

-   m or n denotes 1,

-   Z² preferably denotes —(CH₂)₄—, —CH₂—CH₂—, —CF₂—CF₂—, —CH═CH—,     —CF═CF—, —C≡C—, —O—CH₂—, —O—CF₂— or a single bond,     -   particularly preferably —O—CH₂—, —CH₂—CH₂—, —CF₂—CF₂—, —CF═CF—,         —O—CF₂— or a single bond         and L, R¹ and R² have the meaning given above for formula I, and         L preferably denotes F.

Particular preference is given to compounds of the formula I, preferably selected from the group of the compounds of the formulae I-1 to 1-3, in which

-   n and m both denote 0, and -   L, R¹ and R² have the meaning given above for the corresponding     formula and L preferably denotes F.

Compounds of the formula I containing branched wing groups R¹ and/or R² may occasionally be of importance owing to better solubility in the usual liquid-crystalline base materials, but in particular as chiral dopants if they are optically active. Smectic compounds of this type are suitable as components of ferroelectric materials. Compounds of the formula I having S_(A) phases are suitable, for example, for thermally addressed displays.

If R¹ and/or R² denote an alkyl radical and/or an alkoxy radical, this may be straight-chain or branched. It is preferably straight-chain, has 2, 3, 4, 5, 6 or 7 C atoms and accordingly preferably denotes ethyl, propyl, butyl, pentyl, hexyl, heptyl, ethoxy, propoxy, butoxy, pentoxy, hexyloxy or heptyloxy, furthermore methyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy or tetradecyloxy.

Oxaalkyl or alkoxyalkyl preferably denotes straight-chain 2-oxapropyl (=methoxymethyl), 2-(=ethoxymethyl) or 3-oxabutyl (=2-methoxyethyl), 2-, 3- or 4-oxapentyl, 2-, 3-, 4- or 5-oxahexyl, 2-, 3-, 4-, 5- or 6-oxaheptyl, 2-, 3-, 4-, 5-, 6- or 7-oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonyl, or 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-oxadecyl.

If R¹ and/or R² denote an alkyl radical in which one CH₂ group has been replaced by —CH═CH—, this may be straight-chain or branched. It is preferably straight-chain and has 2 to 10 C atoms. Accordingly, it denotes, in particular, vinyl, prop-1- or -2-enyl, but-1-, -2- or -3-enyl, pent-1-, -2-, -3- or -4-enyl, hex-1-, -2-, -3-, -4- or -5-enyl, hept-1-, -2-, -3-, -4-, -5- or -6-enyl, oct-1-, -2-, -3-, -4-, -5-, -6- or -7-enyl, non-1-, -2-, -3-, -4-, -5-, -6-, -7- or -8-enyl, or dec-1-, -2-, -3-, -4-, -5-, -6-, -7-, -8- or -9-enyl.

If R¹ and/or R² denote an alkyl radical in which one CH₂ group has been replaced by —O— and one has been replaced by —CO—, these are preferably adjacent. These thus contain an acyloxy group —CO—O— or an oxycarbonyl group —O—CO—. These are preferably straight-chain and have 2 to 6 C atoms. Accordingly, they denote, in particular, acetoxy, propionyloxy, butyryloxy, pentanoyloxy, hexanoyloxy, acetoxymethyl, propionyloxymethyl, butyryloxymethyl, pentanoyloxymethyl, 2-acetoxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 3-acetoxypropyl, 3-propionyloxypropyl, 4-acetoxybutyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, butoxycarbonylmethyl, 2-(methoxycarbonyl)ethyl, 2-(ethoxycarbonyl)ethyl, 2-(propoxycarbonyl)ethyl, 3-(methoxycarbonyl)propyl, 3-(ethoxycarbonyl)propyl or 4-(methoxycarbonyl)butyl.

If R¹ and/or R² denote an alkyl radical in which one CH₂ group has been replaced by unsubstituted or substituted —CH═CH— and an adjacent CH₂ group has been replaced by CO or CO—O or O—CO, this may be straight-chain or branched. It is preferably straight-chain and has 4 to 13 C atoms. Accordingly, it denotes, in particular, acryloyloxymethyl, 2-acryloyloxyethyl, 3-acryloyloxypropyl, 4-acryloyloxybutyl, 5-acryloyloxypentyl, 6-acryloyloxyhexyl, 7-acryloyloxyheptyl, 8-acryloyloxyoctyl, 9-acryloyloxynonyl, 10-acryloyloxydecyl, methacryloyloxymethyl, 2-methacryloyloxyethyl, 3-methacryloyloxypropyl, 4-methacryloyloxybutyl, 5-methacryloyloxypentyl, 6-methacryloyloxyhexyl, 7-methacryloyloxyheptyl, 8-methacryloyloxyoctyl or 9-methacryloyloxynonyl.

If R¹ and/or R² denote an alkyl or alkenyl radical which is monosubstituted by CN or CF₃, this radical is preferably straight-chain. The substitution by CN or CF₃ is in any desired position.

If R¹ and/or R² denote an alkyl or alkenyl radical which is at least mono-substituted by halogen, this radical is preferably straight-chain, and halogen is preferably F or Cl. In the case of polysubstitution, halogen is preferably F. The resultant radicals also include perfluorinated radicals. In the case of monosubstitution, the fluorine or chlorine substituent may be in any desired position, but is preferably in the ω-position.

Branched groups generally contain not more than one chain branch. Preferred branched radicals R are isopropyl, 2-butyl (=1-methylpropyl), isobutyl (=2-methylpropyl), 2-methylbutyl, isopentyl (=3-methylbutyl), 2-methylpentyl, 3-methylpentyl, 2-ethylhexyl, 2-propylpentyl, isopropoxy, 2-methylpropoxy, 2-methylbutoxy, 3-methylbutoxy, 2-methylpentoxy, 3-methylpentoxy, 2-ethylhexyloxy, 1-methylhexyloxy and 1-methylheptyloxy.

If R¹ and/or R² represent an alkyl radical in which two or more CH₂ groups have been replaced by —O— and/or —CO—O—, this may be straight-chain or branched. It is preferably branched and has 3 to 12 C atoms. Accordingly, it denotes, in particular, biscarboxymethyl, 2,2-biscarboxyethyl, 3,3-biscarboxypropyl, 4,4-biscarboxybutyl, 5,5-biscarboxypentyl, 6,6-biscarboxyhexyl, 7,7-biscarboxyheptyl, 8,8-biscarboxyoctyl, 9,9-biscarboxynonyl, 10,10-biscarboxydecyl, bis(methoxycarbonyl)methyl, 2,2-bis(methoxycarbonyl)ethyl, 3,3-bis(methoxycarbonyl)propyl, 4,4-bis(methoxycarbonyl)butyl, 5,5-bis(methoxycarbonyl)pentyl, 6,6-bis(methoxycarbonyl)hexyl, 7,7-bis(methoxycarbonyl)heptyl, 8,8-bis(methoxycarbonyl)octyl, bis(ethoxycarbonyl)methyl, 2,2-bis(ethoxycarbonyl)ethyl, 3,3-bis(ethoxycarbonyl)propyl, 4,4-bis(ethoxycarbonyl)butyl or 5,5-bis(ethoxycarbonyl)penyl.

Particular preference is given to compounds of the formula I in which n=0 or 1 and m=0 and R¹ denotes methyl, ethyl, propyl, butyl, pentyl, vinyl, 1E-propenyl, 1E-butenyl or 1E-pentenyl, and to media comprising these compounds. Of these compounds, the alkyl-substituted compounds are particularly preferably employed.

The compounds of the formula I may be in the form of stereoisomers owing to asymmetrically substituted carbon atoms in ring B. The invention relates to all isomers, both in pure form, as a racemate and also as a mixture of diastereomers or enantiomers. Optically active compounds of the formula I can also be used as dopants in liquid-crystal mixtures.

The compounds of the formula I are synthesised (see Schemes I to V) by the processes described in the literature (Houben Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Georg Thieme Verlag, Stuttgart, N.Y., 4th Edn. 1993. Regarding Scheme II, see also DE 10 2004 004 228 (A) and Taugerbeck, M. Klasen-Memmer, Application Number 10 2004 036831.7).

In the following schemes, the compounds of the formula I are abbreviated to compounds 1. Compounds 1b and 1c here are accessible from the lactones 1a. Thus, 1b is obtained either directly by reduction of 1a using sodium borohydride in the presence of boron trifluoride or in two steps by reduction of 1a to the diol 2 and subsequent etherification, for example by treatment with acids or by Mitsunobu reaction with triphenylphosphine and diethyl azodicarboxylate (see Scheme I).

in which, as in the following schemes, unless explicitly indicated otherwise,

-   R¹ and R² each, independently of one another, have the meanings     indicated above for R¹ and R² respectively in the case of formula I     and the other parameters each have the corresponding meanings     indicated above in the case of formula I.

The difluoroether 1c is obtained, for example, either by reaction of the lactones 1a with Lawesson's reagent and subsequent treatment with DAST or NBS in the presence of Ohla's reagent (W. H. Bunnelle, B. R. McKinnis, B. A. Narayanan, J. Org. Chem. 1990, 55, pp. 768-770) or analogously to the process described in A. Taugerbeck, M. Klasen-Memmer, Application Number 10 2004 036831.7 by fluorodesulfuration of dithioorthoesters of type 4 using an oxidant, such as, for example, bromine, NBS, DBH, inter alia, in the presence of a fluoride ion source, such as HF/pyridine complex, triethylamine trishydrogenfluoride, etc. (see Scheme II).

in which n=0 or 1.

The lactones 1a can be prepared as described by S. Sethna, R. Phadke, Org. React. 1953, 7, p. 1 by Pechmann condensation of phenol derivatives or resorcinols with β-ketoesters of type 6 (V. H. Wallingford, A. H. Homeyer, D. M. Jones, J. Am. Chem. Soc. 1941, 63, pp. 2252-2254) and subsequent hydrogenation (Scheme III).

An alternative reduction of the compounds 7 using lithium in ammonia is described in D. J. Collins, A. G. Ghingran, S. B. Rutschmann, Aust. J. Chem. 1989, 42, pp. 1769-1784.

The compounds 7 are also obtainable by the method of P. Sellès, U. Mueller, Org. Lett. 2004, 6, pp. 277-279 by Suzuki coupling from enol triflates 8 (see Scheme IV). The compounds 8 can be obtained from the ketoesters 5 described above by treatment with trifluoromethanesulfonic anhydride in the presence of a base, such as, for example, collidine (E. Piers, H. L. A. Tse, Tetrahedron Lett. 1984, 25, 3155-3158). The boronic acids 9 are accessible, for example, from the corresponding alkyl bromides described in A. Taugerbeck, M. Klasen-Memmer, DE102004004228 by bromine/lithium exchange and subsequent reaction with trimethyl borate.

The compounds 1a are obtained after hydrogenation as an isomer mixture, which can be separated by conventional methods, crystallisation and/or chromatography. Compounds having the 6aR*,8R*,10aS* configuration can be obtained as shown in Scheme V in two additional synthesis steps and by the method of D. J. Collins, A. G. Ghingran, S. B. Rutschmann, Aust. J. Chem. 1989, 42, pp. 1769-1784 by base-catalysed isomerisation, where it may be advantageous firstly to open the lactone ring by saponification analogously to J. M. Fevig et al., Bioorg. Med. Chem. Lett. 1996, 6, pp. 295-300 and to close it again after base-catalysed isomerisation is complete.

Examples of structures of preferred compounds of the formula I, in which R and R′ have the respective meaning given for R¹ and R² respectively under formula I, are given below.

Compounds of the formula I according to the invention may be chiral owing to their molecular structure and can accordingly occur in various enantiomeric forms. They can therefore be in racemic or optically active form.

Since the pharmaceutical efficacy of the racemates or stereoisomers of the compounds according to the invention may differ, it may be desirable to use the enantiomers. In these cases, the end product or alternatively even the intermediates can be separated into enantiomeric compounds by chemical or physical measures known to the person skilled in the art or even employed as such in the synthesis.

In the case of racemic amines, diastereomers are formed from the mixture by reaction with an optically active resolving agent. Suitable resolving agents are, for example, optically active acids, such as the R and S forms of tartaric acid, diacetyltartaric acid, dibenzoyltartaric acid, mandelic acid, malic acid, lactic acid, suitably N-protected amino acids (for example N-benzoylproline or N-benzenesulfonylproline) or the various optically active camphorsulfonic acids. Also advantageous is chromatographic enantiomer separation with the aid of an optically active resolving agent (for example dinitrobenzoylphenylglycine, cellulose triacetate or other derivatives of carbohydrates or chirally derivatised methacrylate polymers immobilised on silica gel). Suitable eluents for this purpose are aqueous or alcoholic solvent mixtures, such as, for example, hexane/isopropanol/acetonitrile, for example in the ratio 82:15:3.

The invention encompasses not only the said compounds, but also mixtures and compositions which, besides these compounds according to the invention, also comprise other pharmacological active ingredients or adjuvants which are able to influence the primary pharmacological action of the compounds according to the invention in the desired manner.

The compounds according to the invention can be employed as medicament active ingredients in human or veterinary medicine, in particular for the prophylaxis or therapy of diseases which can be influenced by the central-nervous action of the compounds.

The compounds according to the invention can particularly preferably be employed for treating sexual disorders or increasing sexual performance, diarrhoea, nicotine dependence, inflammatory CNS diseases (demyelination, viral meningitis, multiple sclerosis, Guillain-Barré syndome) and accident-induced brain injuries or head injuries, appetence disorders, i.e. dependences of various types (drugs, alcohol, sugar), bulimia and any consequences thereof (obesity, diabetes).

They are furthermore active against hypertension or act against anxiety states and/or depression, as sedative, tranquilliser, analgesic, antiemetic or they have an inflammation-inhibiting action.

The central-nervous action can be demonstrated by administration to rats in doses of 0.1-1000 mg/kg, preferably of 1-100 mg/kg. Effects such as reduced spontaneous motor activity are observed, where the requisite dose depends both on the efficacy of the compound and also on the body weight of the experimental animal.

The invention accordingly relates to compounds of the formulae defined above and below and in the claims, including physiologically acceptable salts thereof, as medicaments, diagnostic agents or reagents.

The invention also relates to corresponding pharmaceutical compositions which comprise at least one medicament of the formula I and optionally excipients and/or adjuvants. Suitable excipients are organic or inorganic substances which are suitable for enteral (for example oral), parenteral or topical administration or for administration in the form of an inhalation spray and do not react with the novel compounds, for example water, vegetable oils, benzyl alcohols, alkylene glycols, polyethylene glycols, glycerol triacetate, gelatine, carbohydrates, such as lactose or starch, magnesium stearate, talc and Vaseline. Suitable for oral use are, in particular, tablets, pills, dragees, capsules, powders, granules, syrups, juices or drops, suitable for rectal use are suppositories, suitable for parenteral use are solutions, preferably oily or aqueous solutions, furthermore suspensions, emulsions or implants, and suitable for topical use are ointments, creams or powders. The novel compounds may also be lyophilised and the resultant lyophilisates used, for example, for the preparation of injection preparations. The compositions indicated may have been sterilised and/or comprise adjuvants, such as lubricants, preservatives, stabilisers and/or wetting agents, emulsifiers, salts for modifying the osmotic pressure, buffer substances, colorants, flavours and/or a plurality of further active ingredients, for example one or more vitamins.

For administration as inhalation spray, it is possible to use sprays which comprise the active ingredient either dissolved or suspended in a propellant gas or propellant-gas mixture (for example CO₂). The active ingredient here is advantageously used in micronised form, where one or more additional physiologically tolerated solvents may be present, for example ethanol. Inhalation solutions can be administered with the aid of conventional inhalers.

The substances according to the invention can generally be administered analogously to other, commercially available THC analogues, preferably in doses of between about 0.05 and 500 mg, in particular between 0.5 and 100 mg, per dosage unit. The daily dose is preferably between about 0.01 and 20 mg/kg of body weight. However, the specific dose for each patient depends on a very wide variety of factors, for example on the efficacy of the specific compound employed, on the age, body weight, general state of health, sex, on the diet, on the administration time and method, on the excretion rate, medicament combination and severity of the particular disease to which the therapy applies.

Furthermore, the novel compounds of the formula I can be used in analytical biology and molecular biology.

Specific ligand binding to the receptors is defined as the difference between complete binding and non-specific binding, which is determined in the presence of an excess of unlabelled ligands (see, for example, MUNRO, S., THOMAS, K. L. and ABU-SHAAR, M. (1993), Molecular characterisation of a peripheral receptor for cannabinoids. Nature, 365: 61-65. RINALDI-CARMONA, M., CALANDRA, B., SHIRE, D., BOUABOULA, M., OUSTRIC, D., BARTH, F., CASELLAS, P., FERRARA, P. and LE FUR, G. (1996), Characterisation of two cloned human CB₁ cannabinoid receptors isoform; J. Pharmacol. Exp. Ther., 278:871-878).

The present invention also relates to liquid-crystal media which comprise one or more compound(s) of the formula I.

In a preferred embodiment, the liquid-crystal media in accordance with the present invention comprise

a) one or more dielectrically negative compound(s) of the formula I

-   -   in which     -   Y denotes —CO—, CS, —CH₂— or —CF₂—, preferably CH₂ or CF₂,     -   L denotes H, halogen or CF₃, preferably H, F or Cl, particularly         preferably H or F and very particularly preferably F,

-   -    each, independently of one another and, if present more than         once, also these independently of one another, denote     -   (f) a trans-1,4-cyclohexylene radical, in which, in addition,         one or two non-adjacent CH₂ groups may be replaced by —O— and/or         —S—,     -   (g) a 1,4-cyclohexenylene radical,     -   (h) a 1,4-phenylene radical, in which, in addition, one or two         non-adjacent CH groups may be replaced by N, or     -   (i) naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and         1,2,3,4-tetrahydronaphthalene-2,6-diyl,     -   (j) a radical selected from the group         1,4-bicyclo[2.2.2]octylene, 1,3-bicyclo[1.1.1]pentylene and         spiro[3.3]heptane-2,6-diyl, where in         -   (a) and (b), one or more —CH₂— groups, independently of one             another, may each be replaced by a —CHF— or —CF₂— group, and             in         -   (c) and (d), one or more —CH═ groups, independently of one             another, may each be replaced by a —CF═, —C(CN)═, —C(CH₃)═,             —C(CH₂F)═, —C(CHF₂)═, —C(O—CH₃)═, —C(O—CHF₂)═ or —C(O—CF₃)═             group, preferably a —CF═ group, and preferably denote

-   -    denotes a 1,4-trans-cyclohexane-1,2,4-triyl radical, in which,         in addition, one or two non-adjacent CH₂ groups may be replaced         by —O— and/or —S—, and one or more —CH₂— groups, in each case         independently of one another, may each be replaced by a —CHF— or         —CF₂— group, and the —CH< group may be replaced by a —CF< group,         and which may optionally contain one or two C—C double bonds,         where, in this case, one or more —CH═ groups, independently of         one another, may each be replaced by a —CF═, —C(CN)═, —C(CH₃)═,         —C(CH₂F)═, —C(CHF₂)═, —C(O—CH₃)═, —C(O—CHF₂)═ or —C(O—CF₃)═         group, preferably a —CF═ group,     -   R¹ and R² each, independently of one another, denote H, halogen,         —CN, —SCN, —SF₅, —CF₃, —CHF₂, —CH₂F, —OCF₃, —OCHF₂, an alkyl         group having 1 to 15 C atoms which is monosubstituted by CN or         CF₃ or at least mono-substituted by halogen, where, in addition,         one or more CH₂ groups, in each case independently of one         another, may be replaced by —O—, —S—, —CH═CH—, —CF═CF—, —CF═CH—,         —CH═CF—,

-   -    —CO—, —CO—O—, —O—CO— or —O—CO—O— in such a way that neither O         nor S atoms are linked directly to one another,     -   preferably one of     -   R¹ and R² denotes alkyl or alkoxy having 1 to 12 C atoms,         alkoxyalkyl, alkenyl or alkenyloxy having 2 to 12 C atoms and         the other, independently of the first, likewise denotes alkyl         and alkoxy having 1 to 12 C atoms, alkoxyalkyl, alkenyl or         alkenyloxy having 2 to 12 C atoms or also F, Cl, Br, —CN, —SCN,         —SF₅, —CF₃, —CHF₂, —CH₂F, —OCF₃ or —OCHF₂     -   Z¹ and Z² each, independently of one another and, if present         more than once, also these independently of one another, denote         —CH₂—CH₂—, —CF₂—CF₂—, —CF₂—CH₂—, —CH₂—CF₂—, —CH═CH—, —CF═CF—,         —CF═CH—, —CH═CF—, —C≡C—, —COO—, —OCO—, —CH₂O—, —OCH₂—, —CF₂O—,         —OCF₂—, or a combination of two of these groups, where no two O         atoms are bonded to one another,     -   preferably —(CH₂)₄—, —CH₂—CH₂—, —CF₂—CF₂—, —CH═CH—, —CF═CF—,         —C≡C—, —CH₂O—, —CF₂O— or a single bond,     -   particularly preferably —CH₂O—, —CH₂—CH₂—, —CF₂—CF₂—, —CF═CF—,         —CF₂O— or a single bond, and     -   n and m each denote 0, 1 or 2, where     -   n+m denotes 0, 1, 2 or 3, preferably 0, 1 or 2, particularly         preferably 0 or 1.         b) one or more dielectrically positive compound(s) of the         formula II

-   -   in which     -   R²¹ and R²² each, independently of one another, have the meaning         given above for R¹ in the case of formula I,     -   Z²¹ and Z²² each, independently of one another, have the meaning         given above for Z¹ in the case of formula I,     -   at least one of the rings present

-   -   preferably

-   -    denote(s)

-   -    and the others, in each case independently of one another,         denote

-   -   particularly preferably

-   -    if present, denotes

-   -   L²¹ and L²² both denote C—F or one of the two denotes N and the         other denotes C—F, preferably both denote C—F, and     -   I denotes 0, 1 or 2, preferably 0 or 1;         and optionally         c) one or more dielectrically neutral compounds of the formula         III

-   -   in which     -   R³¹ and R³² each, independently of one another, have the meaning         given above for R¹ in the case of formula I, and     -   Z³¹, Z³² and Z³³ each, independently of one another, denote         —CH₂CH₂—, —CH═CH—, —COO— or a single bond,

-   -    each, independently of one another, denote

-   -   o and p, independently of one another, denote 0 or 1,     -   but preferably     -   R³¹ and R³² each, independently of one another, denote alkyl or         alkoxy having 1-5 C atoms or alkenyl having 2-5 C atoms,

-   -    each, independently of one another, denote

-   -   and very particularly preferably at least two of these rings         denote

-   -   where very particularly preferably two adjacent rings are linked         directly, to be precise preferably

where in the case of the phenylene ring, one or more H atoms, independently of one another, may be replaced by F or CN, preferably by F, and one or two non-adjacent CH₂ groups of the cyclohexylene ring or of one of the cyclohexylene rings may be replaced by O atoms.

The liquid-crystal media preferably comprise one or more compounds of the formula I which contain no biphenyl unit.

The liquid-crystal media particularly preferably comprise one or more compounds of the formula I

in which two adjacent rings are linked directly, to be precise preferably

where in the case of the phenylene ring, one or more H atoms, independently of one another, may be replaced by F or CN, preferably by F, and one or two non-adjacent CH₂ groups of the cyclohexylene ring or of one of the cyclohexylene rings may be replaced by O atoms.

In a preferred embodiment, which may be identical with the embodiments just described, the liquid-crystal media comprise one or more compounds selected from the group of the compounds of the formula I-3.

The liquid-crystal medium preferably comprises one or more compounds selected from the group of the compounds of the formulae II-1 to II-3

in which R²¹, R²², Z¹², Z²²,

and I each have the meaning given above in the case of formula II. Preferably, R²¹ is alkyl, preferably having 1-5 C atoms, R²¹ is alkyl or alkoxy, preferably each having 1 to 5 C atoms, and Z²² and Z²¹, if present, denote a single bond.

The liquid-crystal medium particularly preferably comprises one or more compounds selected from the group of the compounds of the formulae III-1 to III-3:

in which R³¹, R³², Z³¹, Z³²,

each have the meaning given above in the case of formula III.

The liquid-crystal medium particularly preferably comprises one or more compounds selected from the group of the compounds of the formulae III-1a to III-1d, III-1e, III-2a to III-2g, III-3a to III-3d and III-4-a:

in which n and m each, independently of one another, denote 1 to 5, and o and p each, independently both thereof and of one another, denote 0 to 3,

in which R³¹ and R³³ each have the meaning indicated above under formula III, preferably that under formula III-1, and the phenyl rings, in particular in the case of compounds III-2g and III-3c, may optionally be fluorinated, but not in such a way that the compounds are identical with those of the formula II and its sub-formulae. Preferably, R³¹ is n-alkyl having 1 to 5 C atoms, particularly preferably having 1 to 3 C atoms, and R³² is n-alkyl or n-alkoxy having 1 to 5 C atoms or alkenyl having 2 to 5 C atoms. Of these, particular preference is given to compounds of the formulae III-1a to III-1d.

Preferred fluorinated compounds of the formulae III-2g and III-3c are the compounds of the formulae III-2g′ and III-3c′

in which R³¹ and R³³ each have the meaning indicated above under formula III, preferably the meaning indicated under formula III-2g or III-3c.

In the present application, the term compounds is taken to mean both one compound and a plurality of compounds, unless expressly stated otherwise.

The liquid-crystal media according to the invention preferably have nematic phases of in each case from at least −20° C. to 80° C., preferably from −30° C. to 85° C. and very particularly preferably from −40° C. to 100° C. The term “have a nematic phase” here is taken to mean firstly that no smectic phase and no crystallisation are observed at low temperatures at the corresponding temperature and secondly also that no clearing occurs on heating from the nematic phase. The investigation at low temperatures is carried out in a flow viscometer at the corresponding temperature and checked by storage in test cells having a layer thickness corresponding to the electro-optical application for at least 100 hours. At high temperatures, the clearing point is measured in capillaries by conventional methods.

Furthermore, the liquid-crystal media according to the invention are characterised by low optical anisotropy values.

The term “alkyl” preferably encompasses straight-chain and branched alkyl groups having 1 to 7 carbon atoms, in particular the straight-chain groups methyl, ethyl, propyl, butyl, pentyl, hexyl and heptyl. Groups having 2 to 5 carbon atoms are generally preferred.

The term “alkenyl” preferably encompasses straight-chain and branched alkenyl groups having 2 to 7 carbon atoms, in particular the straight-chain groups. Particularly preferred alkenyl groups are C₂- to C₇₋1E-alkenyl, C₄- to C₇₋3E-alkenyl, C₅- to C₇₋4-alkenyl, C₆- to C₇₋5-alkenyl and C₇₋6-alkenyl, in particular C₂- to C₇₋1 E-alkenyl, C₄- to C₇₋3E-alkenyl and C₅- to C₇₋4-alkenyl. Examples of further preferred alkenyl groups are vinyl, 1E-propenyl, 1E-butenyl, 1E-pentenyl, 1E-hexenyl, 1E-heptenyl, 3-butenyl, 3E-pentenyl, 3E-hexenyl, 3E-heptenyl, 4-pentenyl, 4Z-hexenyl, 4E-hexenyl, 4Z-heptenyl, 5-hexenyl, 6-heptenyl and the like. Groups having up to 5 carbon atoms are generally preferred.

The term “fluoroalkyl” preferably encompasses straight-chain groups having a terminal fluorine, i.e. fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl and 7-fluoroheptyl. However, other positions of the fluorine are not excluded.

The term “oxaalkyl” or “alkoxyalkyl” preferably encompasses straight-chain radicals of the formula C_(n)H_(2n+1)—O—(CH₂)_(m), in which n and m each, independently of one another, denote 1 to 6. Preferably, n is 1 and m is 1 to 6.

Compounds containing a vinyl end group and compounds containing a methyl end group have low rotational viscosity.

In the present application, the term dielectrically positive compounds denotes compounds having a Δ∈ of >1.5, the term dielectrically neutral compounds denotes those in which −1.5≦Δ∈≦1.5, and the term dielectrically negative compounds denotes those having a Δ∈ of <−1.5. The dielectric anisotropy of the compounds is determined here by dissolving 10% of the compounds in a liquid-crystalline host and determining the capacitance of this mixture at 1 kHz in at least one test cell with a layer thickness of about 20 μm having a homeotropic surface alignment and at least one test cell with a layer thickness of about 20 μm having a homogeneous surface alignment. The measurement voltage is typically 0.5 V to 1.0 V, but is always less than the capacitive threshold of the respective liquid-crystal mixture.

The host mixture used for determining the applicationally relevant physical parameters is ZLI-4792 from Merck KGaA, Germany. As an exception, the determination of the dielectric anisotropy of dielectrically negative compounds is carried out using ZLI-2857, likewise from Merck KGaA, Germany. The values for the respective compound to be investigated are obtained from the change in the properties, for example the dielectric constants, of the host mixture after addition of the compound to be investigated and extrapolation to 100% of the compound employed.

The concentration employed for the compound to be investigated is 10%. If the solubility of the compound to be investigated is inadequate for this purpose, the concentration employed is, by way of exception, halved, i.e. reduced to 5%, 2.5%, etc., until the concentration is below the solubility limit.

The term threshold voltage usually relates to the optical threshold for 10% relative contrast (V₁₀). In relation to the liquid-crystal mixtures of negative dielectric anisotropy, however, the term threshold voltage is used in the present application for the capacitive threshold voltage (V₀), also known as the Freedericksz threshold, unless explicitly stated otherwise.

All concentrations in this application, unless explicitly stated otherwise, are indicated in percent by weight and relate to the corresponding mixture as a whole. All physical properties are and have been determined in accordance with “Merck Liquid Crystals, Physical Properties of Liquid Crystals”, status November 1997, Merck KGaA, Germany, and apply to a temperature of 20° C., unless explicitly stated otherwise. An is determined at 589 nm and Δ∈ at 1 kHz.

In the case of the liquid-crystal media of negative dielectric anisotropy, the threshold voltage was determined as the capacitive threshold V₀ in cells with a liquid-crystal layer aligned homeotropically by means of lecithin.

The liquid-crystal media according to the invention may, if necessary, also comprise further additives and optionally also chiral dopants in the conventional amounts. The amount of these additives employed is in total from 0% to 10%, based on the amount of the mixture as a whole, preferably from 0.1% to 6%. The concentrations of the individual compounds employed are in each case preferably from 0.1 to 3%. The concentration of these and similar additives is not taken into account when indicating the concentrations and the concentration ranges of the liquid-crystal compounds in the liquid-crystal media.

The compositions consist of a plurality of compounds, preferably 3 to 30, particularly preferably 6 to 20 and very particularly preferably 10 to 16 compounds, which are mixed in a conventional manner. In general, the desired amount of the components used in lesser amount is dissolved in the components making up the principal constituent, advantageously at elevated temperature. If the selected temperature is above the clearing point of the principal constituent, the completion of the dissolution process is particularly easy to observe. However, it is also possible to prepare the liquid-crystal mixtures in other conventional ways, for example using pre-mixes or from so-called “multibottle” systems.

By means of suitable additives, the liquid-crystal phases according to the invention can be modified in such a way that they can be employed in any type of display and in particular of ECB displays and IPS displays that has been disclosed hitherto.

The examples below serve to illustrate the invention without representing a restriction. In the examples, the melting point T(C,N), the transition from the smectic (S) phase to the nematic (N) phase T(S,N) and the clearing point T(N,I) of a liquid-crystal substance are indicated in degrees Celsius. The various smectic phases are characterised by corresponding suffixes.

The percentages above and below are, unless explicitly stated otherwise, percent by weight, and the physical properties are the values at 20° C., unless explicitly stated otherwise.

All the temperature values indicated in this application are ° C. and all temperature differences are correspondingly differential degrees, unless explicitly stated otherwise.

In the synthesis examples and schemes, the abbreviations have the following meanings:

-   DAST diethylaminosulfur trifluoride, -   DBH dibromodimethylhydantoin, -   DEAD diethyl azodicarboxylate, -   MTB ether methyl tert-butyl ether, -   NBS N-bromosuccinimide, -   THF tetrahydrofuran.

In the present application and in the examples below, the structures of the liquid-crystal compounds are indicated by means of acronyms, the trans-formation into chemical formulae taking place in accordance with Tables A and B below. All radicals C_(n)H_(2n+1) and C_(m)H_(2m+1) are straight-chain alkyl radicals having n and m C atoms respectively. The coding in Table B is self-evident. In Table A, only the acronym for the parent structure is indicated. In individual cases, the acronym for the parent structure is followed, separated by a dash, by a code for the substituents R¹, R², L¹, L² and L³:

Code for R¹, R², L¹, L², L³ R¹ R² L¹ L² L³ nm C_(n)H_(2n+1) C_(m)H_(2m+1) H H H nOm C_(n)H_(2n+1) OC_(m)H_(2m+1) H H H nO.m OC_(n)H_(2n+1) C_(m)H_(2m+1) H H H nmFF C_(n)H_(2n+1) C_(m)H_(2m+1) F H F nOmFF C_(n)H_(2n+1) OC_(m)H_(2m+1) F H F nO.mFF OC_(n)H_(2n+1) C_(m)H_(2m+1) F H F nO.OmFF OC_(n)H_(2n+1) OC_(m)H_(2m+1) F H F n C_(n)H_(2n+1) CN H H H nN.F C_(n)H_(2n+1) CN F H H nN.F.F C_(n)H_(2n+1) CN F F H nF C_(n)H_(2n+1) F H H H nF.F C_(n)H_(2n+1) F F H H nF.F.F C_(n)H_(2n+1) F F F H nCl C_(n)H_(2n+1) Cl H H H nCl.F C_(n)H_(2n+1) Cl F H H nCl.F.F C_(n)H_(2n+1) Cl F F H nmF C_(n)H_(2n+1) C_(m)H_(2m+1) F H H nCF₃ C_(n)H_(2n+1) CF₃ H H H nOCF₃ C_(n)H_(2n+1) OCF₃ H H H nOCF₃.F C_(n)H_(2n+1) OCF₃ F H H nOCF₃.F.F C_(n)H_(2n+1) OCF₃ F F H nOCF₂ C_(n)H_(2n+1) OCHF₂ H H H nOCF₂.F.F C_(n)H_(2n+1) OCHF₂ F F H nS C_(n)H_(2n+1) NCS H H H rVsN C_(r)H_(2r+1)—CH═CH—C_(s)H_(2s)— CN H H H nEsN C_(r)H_(2r+1)—O—C_(s)H_(2s)— CN H H H nAm C_(n)H_(2n+1) COOC_(m)H_(2m+1) H H H nF.Cl C_(n)H_(2n+1) F Cl H H

TABLE A PYP

PYRP

BCH

CBC

CCH

CCP

CP

CPTP

CEPTP

D

ECCP

CECP

EPCH

HP

ME

PCH

PDX

PTP

BECH

EBCH

CPC

EHP

BEP

ET

TABLE B CCZU-n-X

CDU-n-X

T3n

K3n

M3n

CGP-n-X

CGU-n-X

CGG-n-X

Inm

CGU-n-X

C-nm

C15

CB15

CBC-nmF

CCN-nm

G3n

CCEPC-nm

CCPC-nm

CH-nm

HD-nm

HH-nm

NCB-nm

OS-nm

CHE

CBC-nmF

ECBC-nm

ECCH-nm

CCH-n1EM

T-nFN

GP-nO-X

CVCC-n-m

CVCP-n-m

CVCVC-n-m

CP-V-N

CC-n-V

CCG-V-F

CPP-nV2-m

CCP-V-m

CCP-V2-m

CPP-V-m

CPP-nV-m

CPP-V2-m

CC-V-V

CC-1V-V

CC-1V-V1

CC-2V-V

CC-2V-V2

CC-2V-V1

CC-V1-V

CC-V1-1V

CC-V2-1V

PCH-n(O)mFF

CCP-n(O)mFF

CPTP-n(O)mFF

Ph-n-(0)mFF

Ph-n0-(0)mFF

BHHO-n-(0)mFF

BHHO-n0-(0)mFF

BFFO-n-(0)mFF

BFFO-n0-(0)mFF

BFO-n-(0)mFF

BFO-n0-(0)mFF

BCOO-n-(0)mFF

BCOO-n0-(0)mFF

BHHO-O1P-n(O)-HFF

BHHO-O1P-n(O)-(O)mFF

BHHO-O1C-n(O)-(O)mFF

EXAMPLES

The following examples are intended to explain the invention without limiting it. Above and below, percentages are percent by weight. All temperatures are indicated in degrees Celsius. Δn denotes the optical anisotropy (589 nm, 20° C.), Δ∈ the dielectric anisotropy (1 kHz, 20° C.), H.R. the voltage holding ratio (at 100° C., after 5 minutes in the oven, 1 V). V₁₀, V₅₀ and V₉₀ (the threshold voltage, mid-grey voltage and saturation voltage respectively) and V₀ (the capacitive threshold voltage) were each determined at 20° C.

Substance Examples Example 1 (3-Ethoxy-6,6-difluoro-8-propyl-6a,7,8,9,10,10a-hexahydro-6H-benzo[c]chromene) 1.1. Preparation of 3-ethoxy-8-propyl-7,8,9,10-tetrahydrobenzo[c]chromen-6-one

16.6 g (78.5 mmol) of methyl 2-oxo-5-propylcyclohexanecarboxylate, 7.65 g (69.5 mmol) of resorcinol and 5.6 ml (6.1 mmol) of phosphoryl chloride are dissolved in 55 ml of toluene, and the mixture is heated under reflux for 3 h. After hydrolysis using water, the deposited precipitate is filtered off with suction, washed with toluene and dried. The product is dissolved in 200 ml of acetone, 20 g (145 mmol) of potassium carbonate and 9.00 g (57.7 mmol) of ethyl iodide are added, and the mixture is heated under reflux for 5 h. The majority of the solvent is removed under reduced pressure, and the residue is taken up in MTB ether/water. The aqueous phase is separated off and extracted with MTB ether. The combined organic phases are washed with water and dried over sodium sulfate. The solvent is removed under reduced pressure, and the crude product is recrystallised from ethanol, giving 3-ethoxy-8-propyl-7,8,9,10-tetrahydrobenzo[c]chromen-6-one as colourless crystals. The melting point is 108° C. The other physical properties are: Δ∈=−7.5 (extrapolated from 5% solution in ZLI-2857), Δn=0.1302 (5% in ZLI-4792).

1.2. Preparation of 3-ethoxy-8-propyl-6a,7,8,9,10,10a-hexahydrobenzo[c]-chromen-6-one

8.60 g (30 mmol) of 3-ethoxy-8-propyl-7,8,9,10-tetrahydrobenzo[c]-chromen-6-one are dissolved in THF and hydrogenated to cessation on palladium/active carbon. The solution is filtered and evaporated, giving 3-ethoxy-8-propyl-6a,7,8,9,10,10a-hexahydrobenzo[c]chromen-6-one as colourless oil.

1.3. Preparation of 10-ethoxy-7-oxa-17-propyl-1,5-dithia-14,15,16,17,18,19-hexahydrodibenzospiro[5.5]nonadecane

29 ml (58 mmol) of a 2M solution of trimethylaluminium in heptane are initially introduced in 35 ml of dichloromethane under nitrogen and cooled to −75° C., and a solution of 2.9 ml (28.5 mmol) of 1,3-propanedithiol in 15 ml of dichloromethane is then added dropwise. The batch is allowed to thaw and cooled to −20° C., and a solution of 8.20 g (26.0 mmol) of 3-ethoxy-8-propyl-6a,7,8,9,10,10a-hexahydrobenzo[c]chromen-6-one in 10 ml of dichloromethane is added dropwise. The batch is left to stir overnight at room temp., added to ice-water and extracted with dichloromethane. The combined organic phases are washed with water and dried over sodium sulfate. The solvent is removed under reduced pressure, and the residue is filtered through silica gel with heptane/MTB (8:2), giving 10.9 g of dithioorthoester as yellow oil, which is employed in the next step without further purification.

1.4. Preparation of 3-ethoxy-6,6-difluoro-6a,7,8,9,10,10a-hexahydro-8-propyl-6H-benzo[c]chromene

4.14 g (10.9 mmol) of dithioorthoester are initially introduced in 300 ml of dichloromethane at −70° C., and 8.9 ml (55 mmol) of triethylamine trishydrofluoride are added. A suspension of 15.7 g (55 mmol) of dibromodimethylhydantoin in 200 ml of dichloromethane is subsequently added in portions, and the batch is left to stir for 2 h. The cooling is then removed, and the solution is added to an ice-cold mixture of 400 ml of 1M sodium hydroxide solution and 20 ml of 39% sodium hydrogensulfite soln. The aqueous phase is separated off and extracted three times with dichloromethane. The combined organic phases are washed with water and dried over sodium sulfate. Removal of the solvent under reduced pressure gives a yellow oil. The latter is taken up in THF and hydrogenated to cessation on a palladium/active carbon catalyst. After filtration, the resultant solution is evaporated under reduced pressure, and the residue is purified by chromatography, giving 3-ethoxy-6,6-difluoro-6a,7,8,9,10,10a-hexahydro-8-propyl-6H-benzo[c]chromene as colourless oil having the following properties.

T_(g)=−39° C.

¹⁹F-NMR (235 MHz, CDCl₃)

δ=−66.8 ppm (d, ²J=155 Hz, 1F, CF₂O), −81.8 (d, ²J=155 Hz, 1F, CF₂O).

MS (EI)

m/e (%)=310 (98) [M⁺], 225 (100).

Example 2 (3-Ethoxy-4,6,6-trifluoro-8-propyl-6a,7,8,9,10,10a-hexahydro-6H-benzo[c]chromene) 2.1. Preparation of 3-ethoxy-4-fluoro-8-propyl-7,8,9,10-tetrahydrobenzo[c]-chromen-6-one

18.2 g (56.6 mmol) of methyl 5-propyl-2-trifluoromethanesulfonyloxycyclohex-1-enecarboxylate, 21.5 g (74.6 mmol) of 4-ethoxy-3-fluoro-2-(2-methoxyethoxymethoxy)benzeneboronic acid, 1.5 ml of water, 33 g (120 mmol) of sodium metaborate, 1.12 g (1.6 mmol) of bis(triphenylphosphine)palladium(II) chloride and 0.1 ml (1.6 mmol) of hydrazinium hydroxide are heated under reflux overnight in 300 ml of tetrahydrofuran. After addition of water, the aqueous phase is separated off and extracted twice with MTB ether. The combined organic phases are washed with saturated sodium chloride soln. and dried over sodium sulfate. The solvent is removed under reduced pressure, and the residue is filtered through silica gel with n-heptane/MTB ether (6:4), giving 3-ethoxy-4-fluoro-8-propyl-7,8,9,10-tetrahydrobenzo[c]chromen-6-one as colourless crystals.

¹³C-NMR (CDCl₃, 75 MHz)

δ=14.2 ppm (CH₃), 14.8 (CH₃), 19.9 (CH₂), 25.4 (CH₂), 27.5 (CH₂), 30.4 (CH₂), 32.6 (CH), 32.7 (CH₂), 38.3 (CH₂), 65.6 (OCH₂CH₃), 109.8 (CH), 114.870 (C), 117.7 (d, J=4.4 Hz, CH), 121.184 (C), 139.7 (d, J=250 Hz, CF), 146.860 (C), 148.384 (C), 148.485 (C), 160.755 (C═O).

2.2. Preparation of 3-ethoxy-4,6,6-trifluoro-8-propyl-6a,7,8,9,10,10a-hexahydro-6H-benzo[c]chromene

3-Ethoxy-4,6,6-trifluoro-8-propyl-6a,7,8,9,10,10a-hexahydro-6H-benzo[c]-chromene is obtained analogously to the synthesis described under 1.

Examples 3 to 120

The following are prepared analogously to Example 1.2.:

Phase sequence T*(N,I)/ No. R¹ R² T/° C. Δε* ° C. 3 CH₃ CH₃ 4 CH₃ C₂H₅ 5 CH₃ n-C₃H₇ 6 CH₃ n-C₄H₉ 7 CH₃ n-C₅H₁₁ 8 CH₃ n-C₆H₁₃ 9 CH₃ n-C₇H₁₅ 10 CH₃ CH₃O 11 CH₃ C₂H₅O 12 CH₃ n-C₃H₇O 13 CH₃ n-C₄H₉O 14 CH₃ CH₂═CH 15 CH₃ E-CH₃—CH═CH 16 CH₃ CH₂═CH—O 17 CH₃ CH₂═CH—CH₂O 18 C₂H₅ CH₃ 19 C₂H₅ C₂H₅ 20 C₂H₅ n-C₃H₇ 21 C₂H₅ n-C₄H₉ 22 C₂H₅ n-C₅H₁₁ 23 C₂H₅ n-C₆H₁₃ 24 C₂H₅ n-C₇H₁₅ 25 C₂H₅ CH₃O 26 C₂H₅ C₂H₅O 27 C₂H₅ n-C₃H₇O 28 C₂H₅ n-C₄H₉O 29 C₂H₅ CH₂═CH 30 C₂H₅ E-CH₃—CH═CH 31 C₂H₅ CH₂═CH—O 32 C₂H₅ CH₂═CH—CH₂O 33 n-C₃H₇ CH₃ 34 n-C₃H₇ C₂H₅ 35 n-C₃H₇ n-C₃H₇ 36 n-C₃H₇ n-C₄H₉ 37 n-C₃H₇ n-C₅H₁₁ 38 n-C₃H₇ n-C₆H₁₃ 39 n-C₃H₇ n-C₇H₁₅ 40 n-C₃H₇ CH₃O 1.2 n-C₃H₇ C₂H₅O 41 n-C₃H₇ n-C₃H₇O 42 n-C₃H₇ n-C₄H₉O 43 n-C₃H₇ CH₂═CH 44 n-C₃H₇ E-CH₃—CH═CH 45 n-C₃H₇ CH₂═CH—O 46 n-C₃H₇ CH₂═CH—CH₂O 47 n-C₄H₉ CH₃ 48 n-C₄H₉ C₂H₅ 49 n-C₄H₉ n-C₃H₇ 50 n-C₄H₉ n-C₄H₉ 51 n-C₄H₉ n-C₅H₁₁ 52 n-C₄H₉ n-C₆H₁₃ 53 n-C₄H₉ n-C₇H₁₅ 54 n-C₄H₉ CH₃O 55 n-C₄H₉ C₂H₅O 56 n-C₄H₉ n-C₃H₇O 57 n-C₄H₉ n-C₄H₉O 58 n-C₄H₉ CH₂═CH 59 n-C₄H₉ E-CH₃—CH═CH 60 n-C₄H₉ CH₂═CH—O 61 n-C₄H₉ CH₂═CH—CH₂O Phase sequence No. R¹ R² T/° C. Δε* 62 CH₃O CH₃ 63 CH₃O C₂H₅ 64 CH₃O n-C₃H₇ 65 CH₃O n-C₄H₉ 66 CH₃O n-C₅H₁₁ 67 CH₃O n-C₆H₁₃ 68 CH₃O n-C₇H₁₅ 69 CH₃O CH₃O 70 CH₃O C₂H₅O 71 CH₃O n-C₃H₇O 72 CH₃O n-C₄H₉O 73 CH₃O CH₂═CH 74 CH₃O E-CH₃—CH═CH 75 CH₃O CH₂═CH—O 76 CH₃O CH₂═CH—CH₂O 77 C₂H₅O CH₃ 78 C₂H₅O C₂H₅ 79 C₂H₅O n-C₃H₇ 80 C₂H₅O n-C₄H₉ 81 C₂H₅O n-C₅H₁₁ C 137 I 82 C₂H₅O n-C₆H₁₃ 83 C₂H₅O n-C₇H₁₅ 84 C₂H₅O CH₃O 85 C₂H₅O C₂H₅O 86 C₂H₅O n-C₃H₇O 87 C₂H₅O n-C₄H₉O 88 C₂H₅O CH₂═CH 89 C₂H₅O E-CH₃—CH═CH 90 C₂H₅O CH₂═CH—O 91 C₂H₅O CH₂═CH—CH₂O 92 CH₂═CH CH₃ 93 CH₂═CH C₂H₅ 94 CH₂═CH n-C₃H₇ 95 CH₂═CH n-C₄H₉ 96 CH₂═CH n-C₅H₁₁ 97 CH₂═CH n-C₆H₁₃ 98 CH₂═CH n-C₇H₁₅ 99 CH₂═CH CH₃O 100 CH₂═CH C₂H₅O 101 CH₂═CH n-C₃H₇O 102 CH₂═CH n-C₄H₉O 103 CH₂═CH CH₂═CH 104 CH₂═CH E-CH₃—CH═CH 105 CH₂═CH CH₂═CH—O 106 CH₂═CH CH₂═CH—CH₂O 107 CH₂═CH—O CH₃ 108 CH₂═CH—O C₂H₅ 109 CH₂═CH—O n-C₃H₇ 110 CH₂═CH—O n-C₄H₉ 111 CH₂═CH—O n-C₅H₁₁ 112 CH₂═CH—O n-C₆H₁₃ 113 CH₂═CH—O n-C₇H₁₅ 114 CH₂═CH—O CH₃O 115 CH₂═CH—O C₂H₅O 116 CH₂═CH—O n-C₃H₇O 117 CH₂═CH—O n-C₄H₉O 118 CH₂═CH—O CH₂═CH 119 CH₂═CH—O E-CH₃—CH═CH 120 CH₂═CH—O CH₂═CH—O 121 CH₂═CH—O CH₂═CH—CH₂O Note: *values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).

Examples 122 to 240

The following are prepared analogously to Example 1.4.:

Phase sequence T*(N,I)/ No. R¹ R² T/° C. Δε* ° C. 122 CH₃ CH₃ 123 CH₃ C₂H₅ 124 CH₃ n-C₃H₇ 125 CH₃ n-C₄H₉ 121 CH₃ n-C₅H₁₁ 126 CH₃ n-C₆H₁₃ 127 CH₃ n-C₇H₁₅ 128 CH₃ CH₃O 129 CH₃ C₂H₅O 130 CH₃ n-C₃H₇O 131 CH₃ n-C₄H₉O 132 CH₃ CH₂═CH 133 CH₃ E-CH₃—CH═CH 134 CH₃ CH₂═CH—O 135 CH₃ CH₂═CH—CH₂O 136 C₂H₅ CH₃ 137 C₂H₅ C₂H₅ 138 C₂H₅ n-C₃H₇ 139 C₂H₅ n-C₄H₉ 140 C₂H₅ n-C₅H₁₁ 141 C₂H₅ n-C₆H₁₃ 142 C₂H₅ n-C₇H₁₅ 143 C₂H₅ CH₃O 144 C₂H₅ C₂H₅O 145 C₂H₅ n-C₃H₇O 146 C₂H₅ n-C₄H₉O 147 C₂H₅ CH₂═CH 148 C₂H₅ E-CH₃—CH═CH 149 C₂H₅ CH₂═CH—O 150 C₂H₅ CH₂═CH—CH₂O 151 n-C₃H₇ CH₃ 152 n-C₃H₇ C₂H₅ 153 n-C₃H₇ n-C₃H₇ 154 n-C₃H₇ n-C₄H₉ 155 n-C₃H₇ n-C₅H₁₁ 156 n-C₃H₇ n-C₆H₁₃ 157 n-C₃H₇ n-C₇H₁₅ 158 n-C₃H₇ CH₃O 159 n-C₃H₇ C₂H₅O 1.4 n-C₃H₇ n-C₃H₇O T_(g) = −39° C. 160 n-C₃H₇ n-C₄H₉O 161 n-C₃H₇ CH₂═CH 162 n-C₃H₇ E-CH₃—CH═CH 163 n-C₃H₇ CH₂═CH—O 164 n-C₃H₇ CH₂═CH—CH₂O 165 n-C₄H₉ CH₃ 166 n-C₄H₉ C₂H₅ 167 n-C₄H₉ n-C₃H₇ 168 n-C₄H₉ n-C₄H₉ 169 n-C₄H₉ n-C₅H₁₁ 170 n-C₄H₉ n-C₆H₁₃ 171 n-C₄H₉ n-C₇H₁₅ 172 n-C₄H₉ CH₃O 173 n-C₄H₉ C₂H₅O 174 n-C₄H₉ n-C₃H₇O 175 n-C₄H₉ n-C₄H₉O 176 n-C₄H₉ CH₂═CH 177 n-C₄H₉ E-CH₃—CH═CH 178 n-C₄H₉ CH₂═CH—O 179 n-C₄H₉ CH₂═CH—CH₂O 180 CH₃O CH₃ 181 CH₃O C₂H₅ 182 CH₃O n-C₃H₇ 183 CH₃O n-C₄H₉ 184 CH₃O n-C₅H₁₁ 185 CH₃O n-C₆H₁₃ 186 CH₃O n-C₇H₁₅ 187 CH₃O CH₃O 188 CH₃O C₂H₅O 189 CH₃O n-C₃H₇O 190 CH₃O n-C₄H₉O 191 CH₃O CH₂═CH 192 CH₃O E-CH₃—CH═CH 193 CH₃O CH₂═CH—O 194 CH₃O CH₂═CH—CH₂O 195 C₂H₅O CH₃ 196 C₂H₅O C₂H₅ 197 C₂H₅O n-C₃H₇ 198 C₂H₅O n-C₄H₉ 199 C₂H₅O n-C₅H₁₁ 201 C₂H₅O n-C₆H₁₃ 202 C₂H₅O n-C₇H₁₅ 203 C₂H₅O CH₃O 204 C₂H₅O C₂H₅O 205 C₂H₅O n-C₃H₇O 206 C₂H₅O n-C₄H₉O 207 C₂H₅O CH₂═CH 208 C₂H₅O E-CH₃—CH═CH 209 C₂H₅O CH₂═CH—O 210 C₂H₅O CH₂═CH—CH₂O Phase sequence No. R¹ R² T/° C. Δε* 211 CH₂═CH CH₃ 212 CH₂═CH C₂H₅ 213 CH₂═CH n-C₃H₇ 214 CH₂═CH n-C₄H₉ 215 CH₂═CH n-C₅H₁₁ 216 CH₂═CH n-C₆H₁₃ 217 CH₂═CH n-C₇H₁₅ 218 CH₂═CH CH₃O 219 CH₂═CH C₂H₅O 220 CH₂═CH n-C₃H₇O 221 CH₂═CH n-C₄H₉O 222 CH₂═CH CH₂═CH 223 CH₂═CH E-CH₃—CH═CH 224 CH₂═CH CH₂═CH—O 225 CH₂═CH CH₂═CH—CH₂O 226 CH₂═CH—O CH₃ 227 CH₂═CH—O C₂H₅ 228 CH₂═CH—O n-C₃H₇ 229 CH₂═CH—O n-C₄H₉ 230 CH₂═CH—O n-C₅H₁₁ 231 CH₂═CH—O n-C₆H₁₃ 232 CH₂═CH—O n-C₇H₁₅ 233 CH₂═CH—O CH₃O 234 CH₂═CH—O C₂H₅O 235 CH₂═CH—O n-C₃H₇O 236 CH₂═CH—O n-C₄H₉O 237 CH₂═CH—O CH₂═CH 238 CH₂═CH—O E-CH₃—CH═CH 239 CH₂═CH—O CH₂═CH—O 240 CH₂═CH—O CH₂═CH—CH₂O Note: *values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).

Examples 241 to 359

The following are prepared analogously to Example 1.2.:

Phase sequence No. R¹ R² T/° C. Δε* 241 CH₃ CH₃ 242 CH₃ C₂H₅ 243 CH₃ n-C₃H₇ 244 CH₃ n-C₄H₉ 245 CH₃ n-C₅H₁₁ 246 CH₃ n-C₆H₁₃ 247 CH₃ n-C₇H₁₅ 248 CH₃ CH₃O 249 CH₃ C₂H₅O 250 CH₃ n-C₃H₇O 251 CH₃ n-C₄H₉O 252 CH₃ CH₂═CH 253 CH₃ E-CH₃—CH═CH 254 CH₃ CH₂═CH—O 255 CH₃ CH₂═CH—CH₂O 256 C₂H₅ CH₃ 257 C₂H₅ C₂H₅ 258 C₂H₅ n-C₃H₇ 259 C₂H₅ n-C₄H₉ 260 C₂H₅ n-C₅H₁₁ 261 C₂H₅ n-C₆H₁₃ 262 C₂H₅ n-C₇H₁₅ 263 C₂H₅ CH₃O 264 C₂H₅ C₂H₅O 265 C₂H₅ n-C₃H₇O 266 C₂H₅ n-C₄H₉O 267 C₂H₅ CH₂═CH 268 C₂H₅ E-CH₃—CH═CH 269 C₂H₅ CH₂═CH—O 270 C₂H₅ CH₂═CH—CH₂O 271 n-C₃H₇ CH₃ 272 n-C₃H₇ C₂H₅ 273 n-C₃H₇ n-C₃H₇ 274 n-C₃H₇ n-C₄H₉ 275 n-C₃H₇ n-C₅H₁₁ 276 n-C₃H₇ n-C₆H₁₃ 277 n-C₃H₇ n-C₇H₁₅ 278 n-C₃H₇ CH₃O 279 n-C₃H₇ C₂H₅O 280 n-C₃H₇ n-C₃H₇O 281 n-C₃H₇ n-C₄H₉O 282 n-C₃H₇ CH₂═CH 283 n-C₃H₇ E-CH₃—CH═CH 284 n-C₃H₇ CH₂═CH—O 285 n-C₃H₇ CH₂═CH—CH₂O 286 n-C₄H₉ CH₃ 287 n-C₄H₉ C₂H₅ 288 n-C₄H₉ n-C₃H₇ 289 n-C₄H₉ n-C₄H₉ 290 n-C₄H₉ n-C₅H₁₁ 291 n-C₄H₉ n-C₆H₁₃ 292 n-C₄H₉ n-C₇H₁₅ 293 n-C₄H₉ CH₃O 294 n-C₄H₉ C₂H₅O 295 n-C₄H₉ n-C₃H₇O 296 n-C₄H₉ n-C₄H₉O 297 n-C₄H₉ CH₂═CH 298 n-C₄H₉ E-CH₃—CH═CH 299 n-C₄H₉ CH₂═CH—O 300 n-C₄H₉ CH₂═CH—CH₂O 300 CH₃O CH₃ 302 CH₃O C₂H₅ 303 CH₃O n-C₃H₇ 304 CH₃O n-C₄H₉ 305 CH₃O n-C₅H₁₁ 306 CH₃O n-C₆H₁₃ 307 CH₃O n-C₇H₁₅ 308 CH₃O CH₃O 309 CH₃O C₂H₅O 310 CH₃O n-C₃H₇O 311 CH₃O n-C₄H₉O 312 CH₃O CH₂═CH 313 CH₃O E-CH₃—CH═CH 314 CH₃O CH₂═CH—O 315 CH₃O CH₂═CH—CH₂O 316 C₂H₅O CH₃ 317 C₂H₅O C₂H₅ 318 C₂H₅O n-C₃H₇ 319 C₂H₅O n-C₄H₉ 320 C₂H₅O n-C₅H₁₁ 241 C₂H₅O n-C₆H₁₃ 321 C₂H₅O n-C₇H₁₅ 322 C₂H₅O CH₃O 323 C₂H₅O C₂H₅O 324 C₂H₅O n-C₃H₇O 325 C₂H₅O n-C₄H₉O 326 C₂H₅O CH₂═CH 327 C₂H₅O E-CH₃—CH═CH 328 C₂H₅O CH₂═CH—O 329 C₂H₅O CH₂═CH—CH₂O 330 CH₂═CH CH₃ 331 CH₂═CH C₂H₅ 332 CH₂═CH n-C₃H₇ 333 CH₂═CH n-C₄H₉ 334 CH₂═CH n-C₅H₁₁ 335 CH₂═CH n-C₆H₁₃ 336 CH₂═CH n-C₇H₁₅ 337 CH₂═CH CH₃O 338 CH₂═CH C₂H₅O 339 CH₂═CH n-C₃H₇O 340 CH₂═CH n-C₄H₉O 341 CH₂═CH CH₂═CH 342 CH₂═CH E-CH₃—CH═CH 343 CH₂═CH CH₂═CH—O 344 CH₂═CH CH₂═CH—CH₂O 345 CH₂═CH—O CH₃ 346 CH₂═CH—O C₂H₅ 347 CH₂═CH—O n-C₃H₇ 348 CH₂═CH—O n-C₄H₉ 349 CH₂═CH—O n-C₅H₁₁ 350 CH₂═CH—O n-C₆H₁₃ 351 CH₂═CH—O n-C₇H₁₅ 352 CH₂═CH—O CH₃O 353 CH₂═CH—O C₂H₅O 354 CH₂═CH—O n-C₃H₇O 355 CH₂═CH—O n-C₄H₉O 356 CH₂═CH—O CH₂═CH 357 CH₂═CH—O E-CH₃—CH═CH 358 CH₂═CH—O CH₂═CH—O 359 CH₂═CH—O CH₂═CH—CH₂O Note: *values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).

Examples 360 to 479

The following are prepared analogously to Example 2.2.:

Phase sequence No. R¹ R² T/° C. Δε* 360 CH₃ CH₃ 361 CH₃ C₂H₅ 362 CH₃ n-C₃H₇ 363 CH₃ n-C₄H₉ 364 CH₃ n-C₅H₁₁ 365 CH₃ n-C₆H₁₃ 366 CH₃ n-C₇H₁₅ 367 CH₃ CH₃O 368 CH₃ C₂H₅O 369 CH₃ n-C₃H₇O 370 CH₃ n-C₄H₉O 371 CH₃ CH₂═CH 372 CH₃ E-CH₃—CH═CH 373 CH₃ CH₂═CH—O 374 CH₃ CH₂═CH—CH₂O 375 C₂H₅ CH₃ 376 C₂H₅ C₂H₅ 377 C₂H₅ n-C₃H₇ 378 C₂H₅ n-C₄H₉ 379 C₂H₅ n-C₅H₁₁ 380 C₂H₅ n-C₆H₁₃ 381 C₂H₅ n-C₇H₁₅ 382 C₂H₅ CH₃O 383 C₂H₅ C₂H₅O 384 C₂H₅ n-C₃H₇O 385 C₂H₅ n-C₄H₉O 386 C₂H₅ CH₂═CH 387 C₂H₅ E-CH₃—CH═CH 388 C₂H₅ CH₂═CH—O 389 C₂H₅ CH₂═CH—CH₂O 390 n-C₃H₇ CH₃ 391 n-C₃H₇ C₂H₅ 392 n-C₃H₇ n-C₃H₇ 393 n-C₃H₇ n-C₄H₉ 394 n-C₃H₇ n-C₅H₁₁ 395 n-C₃H₇ n-C₆H₁₃ 396 n-C₃H₇ n-C₇H₁₅ 397 n-C₃H₇ CH₃O 398 n-C₃H₇ C₂H₅O −12.6 399 n-C₃H₇ n-C₃H₇O 400 n-C₃H₇ n-C₄H₉₀ 401 n-C₃H₇ CH₂═CH 402 n-C₃H₇ E-CH₃—CH═CH 403 n-C₃H₇ CH₂═CH—O 404 n-C₃H₇ CH₂═CH—CH₂O 405 n-C₄H₉ CH₃ 406 n-C₄H₉ C₂H₅ 407 n-C₄H₉ n-C₃H₇ 408 n-C₄H₉ n-C₄H₉ 409 n-C₄H₉ n-C₅H₁₁ 410 n-C₄H₉ n-C₆H₁₃ 411 n-C₄H₉ n-C₇H₁₅ 412 n-C₄H₉ CH₃O 413 n-C₄H₉ C₂H₅O 414 n-C₄H₉ n-C₃H₇O 415 n-C₄H₉ n-C₄H₉O 416 n-C₄H₉ CH₂═CH 417 n-C₄H₉ E-CH₃—CH═CH 418 n-C₄H₉ CH₂═CH—O 419 n-C₄H₉ CH₂═CH—CH₂O 420 CH₃O CH₃ 421 CH₃O C₂H₅ 422 CH₃O n-C₃H₇ 423 CH₃O n-C₄H₉ 424 CH₃O n-C₅H₁₁ 425 CH₃O n-C₆H₁₃ 426 CH₃O n-C₇H₁₅ 427 CH₃O CH₃O 428 CH₃O C₂H₅O 429 CH₃O n-C₃H₇O 430 CH₃O n-C₄H₉O 431 CH₃O CH₂═CH 432 CH₃O E-CH₃—CH═CH 453 CH₃O CH₂═CH—O 434 CH₃O CH₂═CH—CH₂O 435 C₂H₅O CH₃ 436 C₂H₅O C₂H₅ 437 C₂H₅O n-C₃H₇ 438 C₂H₅O n-C₄H₉ 439 C₂H₅O n-C₅H₁₁ 440 C₂H₅O n-C₆H₁₃ 441 C₂H₅O n-C₇H₁₅ 442 C₂H₅O CH₃O 443 C₂H₅O C₂H₅O 444 C₂H₅O n-C₃H₇O 445 C₂H₅O n-C₄H₉O 446 C₂H₅O CH₂═CH 447 C₂H₅O E-CH₃—CH═CH 448 C₂H₅O CH₂═CH—O 449 C₂H₅O CH₂═CH—CH₂O 450 CH₂═CH CH₃ 451 CH₂═CH C₂H₅ 452 CH₂═CH n-C₃H₇ 453 CH₂═CH n-C₄H₉ 454 CH₂═CH n-C₅H₁₁ 455 CH₂═CH n-C₆H₁₃ 456 CH₂═CH n-C₇H₁₅ 457 CH₂═CH CH₃O 458 CH₂═CH C₂H₅O 459 CH₂═CH n-C₃H₇O 460 CH₂═CH n-C₄H₉O 461 CH₂═CH CH₂═CH 462 CH₂═CH E-CH₃—CH═CH 463 CH₂═CH CH₂═CH—O 464 CH₂═CH CH₂═CH—CH₂O 465 CH₂═CH—O CH₃ 466 CH₂═CH—O C₂H₅ 467 CH₂═CH—O n-C₃H₇ 468 CH₂═CH—O n-C₄H₉ 469 CH₂═CH—O n-C₅H₁₁ 470 CH₂═CH—O n-C₆H₁₃ 471 CH₂═CH—O n-C₇H₁₅ 472 CH₂═CH—O CH₃O 473 CH₂═CH—O C₂H₅O 474 CH₂═CH—O n-C₃H₇O 475 CH₂═CH—O n-C₄H₉O 476 CH₂═CH—O CH₂═CH 477 CH₂═CH—O E-CH₃—CH═CH 478 CH₂═CH—O CH₂═CH—O 479 CH₂═CH—O CH₂═CH—CH₂O Note: *values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).

Examples 480 to 509

The following are prepared analogously to Example 1.4.:

in which

Z¹ denotes a single bond. Phase sequence No. R¹ R² T/° C. Δε* 480 CH₃ CH₃ 481 CH₃ C₂H₅ 482 CH₃ n-C₃H₇ 483 C₂H₅ CH₃ 484 C₂H₅ C₂H₅ 485 C₂H₅ n-C₃H₇ 486 n-C₃H₇ CH₃ 487 n-C₃H₇ C₂H₅ 488 n-C₃H₇ n-C₃H₇ 489 n-C₃H₇ n-C₅H₁₁ 490 n-C₅H₁₁ n-C₃H₇ 491 n-C₅H₁₁ n-C₅H₁₁ 492 CH₂═CH CH₃ 493 CH₂═CH C₂H₅ 494 CH₂═CH n-C₃H₇ 495 CH₂═CH CH₂═CH 496 CH₃ CH₂═CH 497 C₂H₅ CH₂═CH 498 n-C₃H₇ CH₂═CH 499 E-CH₃—CH═CH CH₂═CH 500 E-CH₃—CH═CH E-CH₃—CH═CH 501 CH₃ CH₃O 502 CH₃ C₂H₅O 503 CH₃ n-C₃H₇O 504 n-C₃H₇ CH₃O 505 n-C₃H₇ C₂H₅O 586 n-C₃H₇ n-C₃H₇O 507 CH₃O CH₃O 508 C₂H₅O C₂H₅O 509 n-C₃H₇O n-C₃H₇O Note: *values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).

Examples 510 to 539

The following are prepared analogously to Example 1.4.:

Phase sequence Δε* No. R¹ R² T/° C. 510 CH₃ CH₃ 511 CH₃ C₂H₅ 512 CH₃ n-C₃H₇ 513 C₂H₅ CH₃ 514 C₂H₅ C₂H₅ 515 C₂H₅ n-C₃H₇ 516 n-C₃H₇ CH₃ 517 n-C₃H₇ C₂H₅ 518 n-C₃H₇ n-C₃H₇ 519 n-C₃H₇ n-C₅H₁₁ 520 n-C₅H₁₁ n-C₃H₇ 521 n-C₅H₁₁ n-C₅H₁₁ 522 CH₂═CH CH₃ 523 CH₂═CH C₂H₅ 524 CH₂═CH n-C₃H₇ 525 CH₂═CH CH₂═CH 526 CH₃ CH₂═CH 527 C₂H₅ CH₂═CH 528 n-C₃H₇ CH₂═CH 529 E-CH₃—CH═CH CH₂═CH 530 E-CH₃—CH═CH E-CH₃—CH═CH 531 CH₃ CH₃O 532 CH₃ C₂H₅O 533 CH₃ n-C₃H₇O 534 n-C₃H₇ CH₃O 535 n-C₃H₇ C₂H₅O 536 n-C₃H₇ n-C₃H₇O 537 CH₃O CH₃O 538 C₂H₅O C₂H₅O 539 n-C₃H₇O n-C₃H₇O Note: * values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).

Examples 540 to 569

The following are prepared analogously to Example 2.2.:

Phase sequence Δε* No. R¹ R² T/° C. 540 CH₃ CH₃ 541 CH₃ C₂H₅ 542 CH₃ n-C₃H₇ 543 C₂H₅ CH₃ 544 C₂H₅ C₂H₅ 545 C₂H₅ n-C₃H₇ 546 n-C₃H₇ CH₃ 547 n-C₃H₇ C₂H₅ 548 n-C₃H₇ n-C₃H₇ 549 n-C₃H₇ n-C₅H₁₁ 550 n-C₅H₁₁ n-C₃H₇ 551 n-C₅H₁₁ n-C₅H₁₁ 552 CH₂═CH CH₃ 553 CH₂═CH C₂H₅ 554 CH₂═CH n-C₃H₇ 555 CH₂═CH CH₂═CH 556 CH₃ CH₂═CH 557 C₂H₅ CH₂═CH 558 n-C₃H₇ CH₂═CH 559 E-CH₃—CH═CH CH₂═CH 560 E-CH₃—CH═CH E-CH₃—CH═CH 561 CH₃ CH₃O 562 CH₃ C₂H₅O 563 CH₃ n-C₃H₇O 564 n-C₃H₇ CH₃O 565 n-C₃H₇ C₂H₅O 566 n-C₃H₇ n-C₃H₇O 567 CH₃O CH₃O 568 C₂H₅O C₂H₅O 569 n-C₃H₇O n-C₃H₇O Note: * values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).

Examples 570 to 599

The following are prepared analogously to Example 2.2.:

Phase sequence Δε* No. R¹ R² T/° C. 570 CH₃ CH₃ 571 CH₃ C₂H₅ 572 CH₃ n-C₃H₇ 573 C₂H₅ CH₃ 574 C₂H₅ C₂H₅ 575 C₂H₅ n-C₃H₇ 576 n-C₃H₇ CH₃ 577 n-C₃H₇ C₂H₅ 578 n-C₃H₇ n-C₃H₇ 579 n-C₃H₇ n-C₅H₁₁ 580 n-C₅H₁₁ n-C₃H₇ 581 n-C₅H₁₁ n-C₅H₁₁ 582 CH₂═CH CH₃ 583 CH₂═CH C₂H₅ 584 CH₂═CH n-C₃H₇ 585 CH₂═CH CH₂═CH 586 CH₃ CH₂═CH 587 C₂H₅ CH₂═CH 588 n-C₃H₇ CH₂═CH 589 E-CH₃—CH═CH CH₂═CH 590 E-CH₃—CH═CH E-CH₃—CH═CH 591 CH₃ CH₃O 592 CH₃ C₂H₅O 593 CH₃ n-C₃H₇O 594 n-C₃H₇ CH₃O 595 n-C₃H₇ C₂H₅O 596 n-C₃H₇ n-C₃H₇O 597 CH₃O CH₃O 598 C₂H₅O C₂H₅O 599 n-C₃H₇O n-C₃H₇O Note: * values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).

Examples 600 to 629

The following are prepared analogously to Example 1.4.:

Phase sequence Δε* No. R¹ R² T/° C. 600 CH₃ CH₃ 601 CH₃ C₂H₅ 602 CH₃ n-C₃H₇ 603 C₂H₅ CH₃ 604 C₂H₅ C₂H₅ 605 C₂H₅ n-C₃H₇ 606 n-C₃H₇ CH₃ 607 n-C₃H₇ C₂H₅ 608 n-C₃H₇ n-C₃H₇ 609 n-C₃H₇ n-C₅H₁₁ 610 n-C₅H₁₁ n-C₃H₇ 611 n-C₅H₁₁ n-C₅H₁₁ 612 CH₂═CH CH₃ 613 CH₂═CH C₂H₅ 614 CH₂═CH n-C₃H₇ 615 CH₂═CH CH₂═CH 616 CH₃ CH₂═CH 617 C₂H₅ CH₂═CH 618 n-C₃H₇ CH₂═CH 619 E-CH₃-CH═CH CH₂═CH 620 E-CH₃-CH═CH E-CH₃-CH═CH 621 CH₃ CH₃O 622 CH₃ C₂H₅O 623 CH₃ n-C₃H₇O 624 n-C₃H₇ CH₃O 625 n-C₃H₇ C₂H₅O 626 n-C₃H₇ n-C₃H₇O 627 CH₃O CH₃O 628 C₂H₅O C₂H₅O 629 n-C₃H₇O n-C₃H₇O Note: * values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).

Examples 630 to 659

The following are prepared analogously to Example 1.4.:

Phase sequence Δε* No. R¹ R² T/° C. 630 CH₃ CH₃ 631 CH₃ C₂H₅ 632 CH₃ n-C₃H₇ 633 C₂H₅ CH₃ 634 C₂H₅ C₂H₅ 635 C₂H₅ n-C₃H₇ 636 n-C₃H₇ CH₃ 637 n-C₃H₇ C₂H₅ 638 n-C₃H₇ n-C₃H₇ 639 n-C₃H₇ n-C₅H₁₁ 640 n-C₅H₁₁ n-C₃H₇ 641 n-C₅H₁₁ n-C₅H₁₁ 642 CH₂═CH CH₃ 643 CH₂═CH C₂H₅ 644 CH₂═CH n-C₃H₇ 645 CH₂═CH CH₂═CH 646 CH₃ CH₂═CH 677 C₂H₅ CH₂═CH 648 n-C₃H₇ CH₂═CH 649 E-CH₃—CH═CH CH₂═CH 650 E-CH₃—CH═CH E-CH₃—CH═CH 651 CH₃ CH₃O 652 CH₃ C₂H₅O 653 CH₃ n-C₃H₇O 654 n-C₃H₇ CH₃O 655 n-C₃H₇ C₂H₅O 656 n-C₃H₇ n-C₃H₇O 657 CH₃O CH₃O 658 C₂H₅O C₂H₅O 659 n-C₃H₇O n-C₃H₇O Note: * values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).

Examples 660 to 689

The following are prepared analogously to Example 1.4.:

Phase sequence Δε* No. R¹ R² T/° C. 660 CH₃ CH₃ 661 CH₃ C₂H₅ 662 CH₃ n-C₃H₇ 663 C₂H₅ CH₃ 664 C₂H₅ C₂H₅ 665 C₂H₅ n-C₃H₇ 666 n-C₃H₇ CH₃ 667 n-C₃H₇ C₂H₅ 668 n-C₃H₇ n-C₃H₇ 669 n-C₃H₇ n-C₅H₁₁ 670 n-C₅H₁₁ n-C₃H₇ 671 n-C₅H₁₁ n-C₅H₁₁ 672 CH₂═CH CH₃ 673 CH₂═CH C₂H₅ 674 CH₂═CH n-C₃H₇ 675 CH₂═CH CH₂═CH 676 CH₃ CH₂═CH 677 C₂H₅ CH₂═CH 678 n-C₃H₇ CH₂═CH 679 E-CH₃—CH═CH CH₂═CH 680 E-CH₃—CH═CH E-CH₃—CH═CH 681 CH₃ CH₃O 682 CH₃ C₂H₅O 683 CH₃ n-C₃H₇O 684 n-C₃H₇ CH₃O 685 n-C₃H₇ C₂H₅O 686 n-C₃H₇ n-C₃H₇O 687 CH₃O CH₃O 688 C₂H₅O C₂H₅O 689 n-C₃H₇O n-C₃H₇O Note: * values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).

Examples 690 to 719

The following are prepared analogously to Example 1.4.:

Phase sequence Δε* No. R¹ R² T/° C. 690 CH₃ CH₃ 691 CH₃ C₂H₅ 692 CH₃ n-C₃H₇ 693 C₂H₅ CH₃ 694 C₂H₅ C₂H₅ 695 C₂H₅ n-C₃H₇ 696 n-C₃H₇ CH₃ 697 n-C₃H₇ C₂H₅ 698 n-C₃H₇ n-C₃H₇ 699 n-C₃H₇ n-C₅H₁₁ 700 n-C₅H₁₁ n-C₃H₇ 701 n-C₅H₁₁ n-C₅H₁₁ 702 CH₂═CH CH₃ 703 CH₂═CH C₂H₅ 704 CH₂═CH n-C₃H₇ 705 CH₂═CH CH₂═CH 706 CH₃ CH₂═CH 707 C₂H₅ CH₂═CH 708 n-C₃H₇ CH₂═CH 709 E-CH₃—CH═CH CH₂═CH 710 E-CH₃—CH═CH E-CH₃—CH═CH 711 CH₃ CH₃O 712 CH₃ C₂H₅O 713 CH₃ n-C₃H₇O 714 n-C₃H₇ CH₃O 715 n-C₃H₇ C₂H₅O 716 n-C₃H₇ n-C₃H₇O 717 CH₃O CH₃O 718 C₂H₅O C₂H₅O 719 n-C₃H₇O n-C₃H₇O Note: * values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).

Examples 720 to 749

The following are prepared analogously to Example 1.4.:

Phase sequence Δε* No. R¹ R² T/° C. 720 CH₃ CH₃ 721 CH₃ C₂H₅ 722 CH₃ n-C₃H₇ 723 C₂H₅ CH₃ 724 C₂H₅ C₂H₅ 725 C₂H₅ n-C₃H₇ 726 n-C₃H₇ CH₃ 727 n-C₃H₇ C₂H₅ 728 n-C₃H₇ n-C₃H₇ 729 n-C₃H₇ n-C₅H₁₁ 730 n-C₅H₁₁ n-C₃H₇ 731 n-C₅H₁₁ n-C₅H₁₁ 732 CH₂═CH CH₃ 733 CH₂═CH C₂H₅ 734 CH₂═CH n-C₃H₇ 735 CH₂═CH CH₂═CH 736 CH₃ CH₂═CH 737 C₂H₅ CH₂═CH 738 n-C₃H₇ CH₂═CH 739 E-CH₃—CH═CH CH₂═CH 740 E-CH₃—CH═CH E-CH₃—CH═CH 741 CH₃ CH₃O 742 CH₃ C₂H₅O 743 CH₃ n-C₃H₇O 744 n-C₃H₇ CH₃O 745 n-C₃H₇ C₂H₅O 746 n-C₃H₇ n-C₃H₇O 747 CH₃O CH₃O 748 C₂H₅O C₂H₅O 749 n-C₃H₇O n-C₃H₇O Note: * values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).

Examples 750 to 779

The following are prepared analogously to Example 1.4.:

Phase sequence Δε* No. R¹ R² T/° C. 750 CH₃ CH₃ 751 CH₃ C₂H₅ 752 CH₃ n-C₃H₇ 753 C₂H₅ CH₃ 754 C₂H₅ C₂H₅ 755 C₂H₅ n-C₃H₇ 756 n-C₃H₇ CH₃ 757 n-C₃H₇ C₂H₅ 758 n-C₃H₇ n-C₃H₇ 759 n-C₃H₇ n-C₅H₁₁ 760 n-C₅H₁₁ n-C₃H₇ 761 n-C₅H₁₁ n-C₅H₁₁ 762 CH₂═CH CH₃ 763 CH₂═CH C₂H₅ 764 CH₂═CH n-C₃H₇ 765 CH₂═CH CH₂═CH 766 CH₃ CH₂═CH 767 C₂H₅ CH₂═CH 768 n-C₃H₇ CH₂═CH 769 E-CH₃—CH═CH CH₂═CH 770 E-CH₃—CH═CH E-CH₃—CH═CH 771 CH₃ CH₃O 772 CH₃ C₂H₅O 773 CH₃ n-C₃H₇O 774 n-C₃H₇ CH₃O 775 n-C₃H₇ C₂H₅O 776 n-C₃H₇ n-C₃H₇O 777 CH₃O CH₃O 778 C₂H₅O C₂H₅O 779 n-C₃H₇O n-C₃H₇O Note: * values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).

Examples 780 to 809

The following are prepared analogously to Example 1.4.:

Phase sequence Δε* No. R¹ R² T/° C. 780 CH₃ CH₃ 781 CH₃ C₂H₅ 782 CH₃ n-C₃H₇ 783 C₂H₅ CH₃ 784 C₂H₅ C₂H₅ 785 C₂H₅ n-C₃H₇ 786 n-C₃H₇ CH₃ 787 n-C₃H₇ C₂H₅ 788 n-C₃H₇ n-C₃H₇ 789 n-C₃H₇ n-C₅H₁₁ 790 n-C₅H₁₁ n-C₃H₇ 791 n-C₅H₁₁ n-C₅H₁₁ 792 CH₂═CH CH₃ 793 CH₂═CH C₂H₅ 794 CH₂═CH n-C₃H₇ 795 CH₂═CH CH₂═CH 796 CH₃ CH₂═CH 797 C₂H₅ CH₂═CH 798 n-C₃H₇ CH₂═CH 799 E-CH₃—CH═CH CH₂═CH 800 E-CH₃—CH═CH E-CH₃—CH═CH 801 CH₃ CH₃O 802 CH₃ C₂H₅O 803 CH₃ n-C₃H₇O 804 n-C₃H₇ CH₃O 805 n-C₃H₇ C₂H₅O 806 n-C₃H₇ n-C₃H₇O 807 CH₃O CH₃O 808 C₂H₅O C₂H₅O 809 n-C₃H₇O n-C₃H₇O Note: * values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).

Examples 810 to 839

The following are prepared analogously to Example 1.4.:

Phase sequence Δε* No. R¹ R² T/° C. 810 CH₃ CH₃ 811 CH₃ C₂H₅ 812 CH₃ n-C₃H₇ 813 C₂H₅ CH₃ 814 C₂H₅ C₂H₅ 815 C₂H₅ n-C₃H₇ 816 n-C₃H₇ CH₃ 817 n-C₃H₇ C₂H₅ 818 n-C₃H₇ n-C₃H₇ 819 n-C₃H₇ n-C₅H₁₁ 820 n-C₅H₁₁ n-C₃H₇ 821 n-C₅H₁₁ n-C₅H₁₁ 822 CH₂═CH CH₃ 823 CH₂═CH C₂H₅ 824 CH₂═CH n-C₃H₇ 825 CH₂═CH CH₂═CH 826 CH₃ CH₂═CH 827 C₂H₅ CH₂═CH 828 n-C₃H₇ CH₂═CH 829 E-CH₃—CH═CH CH₂═CH 830 E-CH₃—CH═CH E-CH₃—CH═CH 831 CH₃ CH₃O 832 CH₃ C₂H₅O 833 CH₃ n-C₃H₇O 834 n-C₃H₇ CH₃O 835 n-C₃H₇ C₂H₅O 836 n-C₃H₇ n-C₃H₇O 837 CH₃O CH₃O 838 C₂H₅O C₂H₅O 839 n-C₃H₇O n-C₃H₇O Note: * values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).

Mixture Examples

Liquid-crystalline mixtures are prepared and investigated for their applicational properties.

Example M 1

A liquid-crystal mixture having the composition indicated in the following table was prepared and investigated. It has the properties likewise shown in the table.

Composition Compound Conc./ # Abbreviation % by wt. 1 CY-3-O4 7 2 CY-5-O2 5 3 CCY-3-O2 7 4 CCY-4-O2 8 5 CCY-3-O3 7 6 CPY-2-O2 9 7 CPY-3-O2 9 8 PYP-2-3 8 9 PYP-2-4 8 10 CC-5-V 9 11 CC-4-V 6 12 CC-3-V1 6 13 CCH-301 6 14 Comp. 398 5 Σ 100.0 Physical properties T(N,I) = 86° C. n_(e) (20° C., 589 nm) = 1.6161 Δn (20° C., 589 nm) = 0.1207 ε⊥ (20° C., 1 kHz) = 7.3 Δε (20° C., 1 kHz) = −4.2

The liquid-crystal medium has very good applicational properties and can be employed for various VA technologies, such as MVA, PVA, ASV and also for IPS. 

1. A compound of formula I

in which Y denotes CF₂—, L denotes H, halogen or —CF₃,

each, independently of one another and, if present more than once, also these independently of one another, denote a trans-1,4-cyclohexylene radical, in which, in addition, one or two non-adjacent CH₂ groups may be replaced by —O— and/or —S—, a 1,4-cyclohexenylene radical, a 1,4-phenylene radical, in which, in addition, one or two non-adjacent CH groups may be replaced by N, or naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl, 1,4-bicyclo[2.2.2]octylene, 1,3-bicyclo[1.1.1]pentylene or spiro-[3.3]heptane-2,6-diyl, wherein (a) and (b), one or more —CH₂— groups, independently of one another, may each be replaced by a —CHF— or —CF₂— group, and in (c) and (d), one or more —CH═ groups, independently of one another, may each be replaced by a —CF═, —C(CN)═, —C(CH₃)═, —C(CH₂F)═, —C(CHF₂)═, —C(O—CH₃)═, —C(O—CHF₂)═or —C(O—CF₃)═ group,

denotes a 1,4-trans-cyclohexane-1,2,4-triyl radical, in which, in addition, one or more —CH₂—groups, in each case independently of one another, may each be replaced by a —CHF—or —CF₂—group, and the —CH< group may be replaced by a —CF< group, and which may optionally contain one or two C—C double bonds, where, in this case, one or more —CH═ groups, independently of one another, may each be replaced by a —CF═, —C(CN)═, —C(CH₃)═, —C(CH₂F)═, —C(CHF₂)═, —C(O—CH₃)═, —C(O—CHF₂)═ or —C(O—CF₃)═ group, R¹ and R² each, independently of one another, denote H, halogen, —CN, —SCN, —SF₅, —CF₃, —CHF₂, —CH₂F, —OCF₃, —OCHF₂, an alkyl group having 1 to 15 C atoms which is monosubstituted by CN or CF₃ or at least monosubstituted by halogen, where, in addition, one or more CH₂ groups, in each case independently of one another, may be replaced by —O—, —S—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—,

—CO—,—CO—O—,—O—CO— or —O—CO—O—in such a way that neither O nor S atoms are linked directly to one another, Z¹ and Z² each, independently of one another, denote —CH₂—CH₂—, —CF₂—CF₂—, —CF₂—CH₂—, —CH₂—CF₂—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—, —C≡C—, —COO—, —OCO—, —CH₂O—, —OCH₂—, —CF₂O—, —OCF₂—, or a combination of two of these groups, where no two O atoms are bonded to one another, and n and m each denote 0, 1 or 2, where n +m denotes 0, 1, 2 or
 3. 2. The compound according to claim 1, of the formulae I-3


3. The compound according to claim 1, wherein L denotes F.
 4. The compound according to claim 1, wherein Z¹ and Z² both denote a single bond.
 5. A liquid-crystalline medium, comprising one or more compounds of formula I as

in which Y denotes —CO—, —CS—, —CH₂— or —CF₂—, L denotes H, halogen or —CF₃,

each, independently of one another and, if present more than once, also these independently of one another, denote a trans-1,4-cyclohexylene radical, in which, in addition, one or two non-adjacent CH₂ groups may be replaced by —O— and/or —S—, a 1,4-cyclohexenylene radical, a 1,4-phenylene radical, in which, in addition, one or two non-adjacent CH groups may be replaced by N, or naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl, 1,4-bicyclo[2.2.2]octylene, 1,3-bicyclo[1.1.1]pentylene or spiro-[3.3]heptane-2,6-diyl, wherein (a) and (b), one or more —CH₂— groups, independently of one another, may each be replaced by a —CHF— or —CF₂— group, and in (c) and (d), one or more —CH═ groups, independently of one another, may each be replaced by a —CF═, —C(CN)═, —C(CH₃)═, —C(CH₂F)═, —C(CHF₂)═, —C(O—CH₃)═, —C(O—CHF₂)═ or —C(O—CF₃)═ group,

denotes a 1,4-trans-cyclohexane-1,2,4-triyl radical, in which, in addition, one or more —CH₂— groups, in each case independently of one another, may each be replaced by a —CHF— or —CF₂— group, and the —CH< group may be replaced by a —CF< group, and which may optionally contain one or two C—C double bonds, where, in this case, one or more —CH═ groups, independently of one another, may each be replaced by a —CF═, —C(CN)═, —C(CH₃)═, —C(CH₂F)═, —C(CHF₂)═, —C(O—CH₃)═, —C(O—CHF₂)═ or —C(O—CF₃)═ group, R¹ and R² each, independently of one another, denote H, halogen, —CN, —SCN, —SF₅, —CF₃ —CHF₂ —CH₂F —OCF₃ —OCHF₂, an alkyl group having 1 to 15 C atoms which is monosubstituted by CN or CF₃ or at least monosubstituted by halogen, where, in addition, one or more CH₂ groups, in each case independently of one another, may be replaced by —O—, —S—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—,

—CO—, —CO—O—, —O—CO—or —O13 CO—O—in such a way that neither O nor S atoms are linked directly to one another, Z¹ and Z² each, independently of one another, denote —CH₂—CH₂—, —CF₂—CF₂—, —CF₂—CH₂—, —CH₂—CF₂—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—, —C≡C—, —COO—, —OCO—, —CH₂O—, —OCH₂—, —CF₂O—, —OCF₂—, or a combination of two of these groups, where no two O atoms are bonded to one another, and n and m each denote 0, 1 or 2, where n +m denotes 0, 1, 2 or
 3. 6. A liquid-crystalline medium, comprising a nematic phase and having one or more compounds of formula I as defined in claim
 5. 7. The liquid-crystalline medium according to claim 5, comprising one or more dielectrically negative compound(s) of formula II

in which R²¹ and R²² each, independently of one another, have the meaning given for R¹ in the case of formula I, Z²¹ and Z²² each, independently of one another, have the meaning given for Z¹ in the case of formula I,

each, independently of one another, denote

L¹ and L² both denote C—F or one of the two denotes N and the other denotes C—F, and 1 denotes 0 or
 1. 8. The liquid-crystalline medium according to claim 7, comprising one or more compound(s) of formula II-1

in which R²¹, R²², Z¹², Z²²,

and 1 have the meaning given in claim
 7. 9. An electro-optical display comprising a liquid-crystal medium according to claim
 5. 10. The display according to claim 9, which is a VAN LCD.
 11. A method for the inhibition of cannabinoid receptor, comprising administering to a host in need thereof an effective amount of a compound

in which Y denotes —CO—, —CS—, —CH₂— or —CF₂—, L denotes H, halogen or —CF₃,

each, independently of one another and, if present more than once, also these independently of one another, denote a trans-1,4-cyclohexylene radical, in which, in addition, one or two non-adjacent CH₂ groups may be replaced by —O— and/or —S—, a 1,4-cyclohexenylene radical, a 1,4-phenylene radical, in which, in addition, one or two non-adjacent CH groups may be replaced by N, or naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4- tetrahydronaphthalene -2,6-diyl, 1,4-bicyclo[2.2.21]octylene, 1,3-bicyclo[1.1.1]pentylene or spiro-[3.3]heptane-2,6-diyl, wherein (a) and (b), one or more —CH₂— groups, independently of one another, may each be replaced by a —CHF— or —CF₂— group, and in (c) and (d), one or more —CH═ groups, independently of one another, may each be replaced by a —CF═, —C(CN)═, —C(CH₃)═, —C(CH₂F)═, —C(CHF₂)═, —C(O—CH₃)═, —C(O—CHF₂)═ or —C(O—CF₃)═ group,

denotes a 1,4-trans-cyclohexane-1,2,4-triyl radical, in which, in addition, one or more —CH₂— groups, in each case independently of one another, may each be replaced by a —CHF— or —CF₂— group, and the —CH< group may be replaced by a —CF< group, and which may optionally contain one or two C—C double bonds, where, in this case, one or more —CH═ groups, independently of one another, may each be replaced by a —CF═, —C(CN)═, —C(CH₃)═, —C(CH₂F)═, —C(CHF₂)═, —C(O—CH₃)═, —C(O—CHF₂)═ or —C(O—CF₃)═ group, R¹ and R² each, independently of one another, denote H, halogen, —CN, —SCN, —SF₅, —CF₃,—CHF₂, —CH₂F, —OCF₃, —OCHF₂, an alkyl group having 1 to 15 C atoms which is monosubstituted by CN or CF₃ or at least monosubstituted by halogen, where, in addition, one or more CH₂ groups, in each case independently of one another, may be replaced by —O—, —S—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—,

—CO—, —CO—O—, —O—CO— or —O—CO—O— in such a way that neither O nor S atoms are linked directly to one another, Z¹ and Z² each, independently of one another, denote —CH₂——CH₂—,—CF₂—CF₂—, —CF₂—CH₂—, —CH₂—CF₂—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—, —C≡C—, —COO—, —OCO—, —CH₂O—, —OCH₂—, —CF₂O—, —OCF₂—, or a combination of two of these groups, where no two O atoms are bonded to one another, and n and m each denote 0, 1 or 2, where n +m denotes 0, 1, 2 or
 3. or a salt or solvate thereof.
 12. A pharmaceutical composition, comprising at least one compound of formula I according to claim 1 and/or a physiologically acceptable salt or solvate thereof.
 13. A method for the treatment or prophylaxis of diseases or symptoms which can be influenced by inhibition of cannabinoid receptors comprising administering a compound of formula I

in which Y denotes —CO—, —CS—, —CH₂— or —CF₂—, L denotes H, halogen or —CF₃,

each, independently of one another and, if present more than once, also these independently of one another, denote a trans-1,4-cyclohexylene radical, in which, in addition, one or two non-adjacent CH₂ groups may be replaced by —O— and/or —S—, a 1,4-cyclohexenylene radical, a 1,4-phenylene radical, in which, in addition, one or two non-adjacent CH groups may be replaced by N, or naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4- tetrahydronaphthalene -2,6-diyl, 1,4-bicyclo[2.2.2]octylene, 1,3-bicyclo[1.1.1]pentylene or spiro-[3.3]heptane-2,6-diyl, wherein (a) and (b), one or more —CH₂— groups, independently of one another, may each be replaced by a —CHF— or —CF₂— group, and in (c) and (d), one or more —CH═ groups, independently of one another, may each be replaced by a —CF═, —C(CN)═, —C(CH₃)═, —C(CH₂F)═, —C(CHF₂)═, —C(O—CH₃)═, —C(O—CHF₂)═ or —C(O—CF₃)═ group,

denotes a 1,4-trans-cyclohexane-1,2,4-triyl radical, in which, in addition, one or more —CH₂— groups, in each case independently of one another, may each be replaced by a —CHF— or —CF₂— group, and the —CH< group may be replaced by a —CF< group, and which may optionally contain one or two C—C double bonds, where, in this case, one or more —CH═ groups, independently of one another, may each be replaced by a —CF═, —C(CN)═, —C(CH₃)═, —C(CH₂F)═, —C(CHF₂)═, —C(O—CH₃)═, —C(O—CHF₂)═ or —C(O—CF₃)═ group, R¹ and R² each, independently of one another, denote H, halogen, —CN, —SCN, —SF₅, —CF₃, —CHF₂ , —CH₂F, —OCF₃, —OCHF₂, an alkyl group having 1 to 15 C atoms which is monosubstituted by CN or CF₃ or at least monosubstituted by halogen, where, in addition, one or more CH₂ groups, in each case independently of one another, may be replaced by —O—, —S—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—,

—CO—, —CO—O—, —O—CO— or —O—CO—O— in such a way that neither O nor S atoms are linked directly to one another, Z¹ and Z² each, independently of one another, denote —CH₂—CH_(2—, —CF) ₂—CF₂—, —CF₂—CH₂—, —CH₂—CF₂—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—, —C≡C—, —COO—, —OCO—, —CH₂O—, —OCH₂—, —CF₂O—, —OCF₂—, or a combination of two of these groups, where no two O atoms are bonded to one another, and n and m each denote 0, 1 or 2, where n +m denotes 0, 1, 2 or
 3. and/or a physiologically acceptable salt or solvate thereof.
 14. A method of claim 13 comprising treatment or prophylaxis of psychoses, anxiety disorders, depression, aprosexia, memory disorders, cognitive disorders, loss of appetite, obesity, addiction, drug dependence and neurological disorders, such as neurodegenerative processes, dementia, dystonia, muscle spasms, tremor, epilepsy, multiple sclerosis, traumatic brain injuries, strokes, Parkinson's, Alzheimer's, Huntington's disease, Tourette's syndrome, cerebral ischaemia, cerebral apoplexy, craniocerebral trauma, spinal cord injuries, neuroinflammatory diseases, cerebral arteriosclerosis, viral encephalitis, diseases associated with demyelination, for the treatment of pain, neuropathic pain diseases, diseases in which cannabinoid neurotransmission plays a role, septic shock, glaucoma, cancer, diabetes, vomiting, nausea, asthma, respiratory tract diseases, gastrointestinal diseases, gastric ulcers, diarrhoea or cardiovascular diseases.
 15. A compound according to claim 1, wherein

is


16. A method for the treatment or prophylaxis of diseases or symptoms which can be influenced by inhibition of cannabinoid receptors comprising administering a compound of formula I

in which Y denotes —CO—, —CS—, —CH₂— or —CF₂—, L denotes H, halogen or —CF₃,

each, independently of one another and, if present more than once, also these independently of one another, denote a trans-1,4-cyclohexylene radical, in which, in addition, one or two non-adjacent CH₂ groups may be replaced by —O— and/or —S—, a 1,4-cyclohexenylene radical, a 1,4-phenylene radical, in which, in addition, one or two non-adjacent CH groups may be replaced by N, or naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl, 1,4-bicyclo[2.2.2]octylene, 1,3-bicyclo[1.1.1]pentylene or spiro-[3.3]heptane-2,6-diyl, wherein (a) and (b), one or more —CH₂— groups, independently of one another, may each be replaced by a —CHF— or —CF₂— group, and in (c) and (d), one or more —CH═ groups, independently of one another, may each be replaced by a —CF═, —C(CN)═, —C(CH₃)═, —C(CH₂F)═, —C(CHF₂)═, —C(O—CH₃)═, —C(O—CHF₂)═ or —C(O—CF₃)═ group,

denotes a 1,4-trans-cyclohexane-1,2,4-triyl radical, in which, in addition, one or two non-adjacent CH₂ groups may be replaced by —O— and/or —S—, and one or more —CH₂— groups, in each case independently of one another, may each be replaced by a —CHF— or —CF₂— group, and the —CH< group may be replaced by a —CF< group, and which may optionally contain one or two C—C double bonds, where, in this case, one or more —CH═ groups, independently of one another, may each be replaced by a —CF═, —C(CN)═, —C(CH₃)═, —C(CH₂F)═, —C(CHF₂)═, —C(O—CH₃)═, —C(O—CHF₂)═ or —C(O—CF₃)═ group, R¹ and R² each, independently of one another, denote H, halogen, —CN, —SCN, —SF₅, —CF₃, —CHF₂, —CH₂F, —OCF₃, —OCHF₂, an alkyl group having 1 to 15 C atoms which is monosubstituted by CN or CF₃ or at least monosubstituted by halogen, where, in addition, one or more CH₂ groups, in each case independently of one another, may be replaced by —O—, —S—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—,

—CO—, —CO—O—, —O—CO— or —O—CO—O— in such a way that neither O nor S atoms are linked directly to one another, Z¹ and Z² each, independently of one another, denote —CH₂—CH₂—, —CF₂—CF₂—, —CF₂—CH₂—, —CH₂—CF₂—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—, —COO—, —O—, —CH₂O—, —OCH₂—, —CF₂O—, —OCF₂—, or a combination of two of these groups, where no two O atoms are bonded to one another, and n and m each denote 0, 1 or 2, where n +m denotes 0, 1, 2 or
 3. 17. A method for the treatment or prophylaxis of psychoses, anxiety disorders, depression, aprosexia, memory disorders, cognitive disorders, loss of appetite, obesity, addiction, drug dependence and neurological disorders, such as neurodegenerative processes, dementia, dystonia, muscle spasms, tremor, epilepsy, multiple sclerosis, traumatic brain injuries, strokes, Parkinson's, Alzheimer's, Huntington's disease, Tourette's syndrome, cerebral ischaemia, cerebral apoplexy, craniocerebral trauma, spinal cord injuries, neuroinflammatory diseases, cerebral arteriosclerosis, viral encephalitis, diseases associated with demyelination, for the treatment of pain, neuropathic pain diseases, diseases in which cannabinoid neurotransmission plays a role, septic shock, glaucoma, cancer, diabetes, vomiting, nausea, asthma, respiratory tract diseases, gastrointestinal diseases, gastric ulcers, diar-rhoea or cardiovascular diseases, comprising administering to a host in need thereof a compound of formula I and

in which Y denotes —CO—, —CS—, —CH₂— or —CF₂—, L denotes H, halogen or —CF₃,

each, independently of one another and, if present more than once, also these independently of one another, denote a trans-1,4-cyclohexylene radical, in which, in addition, one or two non-adjacent CH₂ groups may be replaced by —O— and/or —S—, a 1,4-cyclohexenylene radical, a 1,4-phenylene radical, in which, in addition, one or two non-adjacent CH groups may be replaced by N, or naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl, 1,4-bicyclo[2.2.2]octylene, 1,3-bicyclo[1.1.1]pentylene or spiro-[3.3]heptane-2,6-diyl, wherein (a) and (b), one or more —CH₂— groups, independently of one another, may each be replaced by a —CHF— or —CF₂— group, and in (c) and (d), one or more —CH═ groups, independently of one another, may each be replaced by a —CF═, —C(CN)═, —C(CH₃)═, —C(CH₂F)═, —C(CHF₂)═, —C(O—CH₃)═, —C(O—CHF₂)═ or —C(O—CF₃)═ group,

denotes a 1,4-trans-cyclohexane-1,2,4-triyl radical, in which, in addition, one or two non-adjacent CH₂ groups may be replaced by —O— and/or —S—, and one or more —CH₂— groups, in each case independently of one another, may each be replaced by a —CHF— or —CF₂— group, and the —CH< group may be replaced by a —CF< group, and which may optionally contain one or two C—C double bonds, where, in this case, one or more —CH═ groups, independently of one another, may each be replaced by a —CF═, —C(CN)═, —C(CH₃)═, —C(CH₂F)═, —C(CHF₂)═, —C(O—CH₃)═, —C(O—CHF₂)═ or —C(O—CF₃)═ group, preferably a —CF═ group, R¹ and R² each, independently of one another, denote H, halogen, —CN, —SCN, —SF₅, —CF₃, —CHF₂, —CH₂F, —OCF₃, —OCHF₂, an alkyl group having 1 to 15 C atoms which is monosubstituted by CN or CF₃ or at least monosubstituted by halogen, where, in addition, one or more CH₂ groups, in each case independently of one another, may be replaced by —O—, —S—, —CH═CH—, —C0F═CF—, —CF═CH—, —CH═CF—,

—CO—, —CO—O—, —O—CO— or —O—CO—O— in such a way that neither O nor S atoms are linked directly to one another, Z¹ and Z² each, independently of one another, denote —CH₂—CH₂—, —CF₂—CF₂—, —CF₂—CH₂—, —CH₂—CF₂—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—, —C≡C—, —COO—, —OCO—, —CH₂O—, —OCH₂—, —CF₂O—, —OCF₂—, or a combination of two of these groups, where no two O atoms are bonded to one another, and n and m each denote 0, 1 or 2, where n +m denotes 0, 1, 2 or
 3. 